Alkyl carbonate derivatives of furanics: a family of
bio-based stable compounds
Angel Gabriel Sathicq,a Mattia Annatelli,b Iskandar Abdullah,c Gustavo Romanellia,d and Fabio Aricòb,*
aCentro de Investigación y Desarrollo en Ciencias Aplicadas “Dr. Jorge J. Ronco” (CINDECA)
CCT-La Plata-CONICET, Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata 47°N 257, B1900AJK La Plata (Argentina)
bDepartment of Environmental Sciences, Informatics and Statistics, Ca’ Foscari University,
campus scientifico, Via Torino 155, 30172 Venezia Mestre.
cDepartment of Chemistry, Faculty of Science, Universiti Malaya, 50603 Kuala Lumpur, W.
Persekutuan Kuala Lumpur, Malaysia
bCISAV. Cátedra de Química Orgánica, Facultad de Ciencias Agrarias y Forestales, Universidad
Nacional de La Plata, Calles 60 y 119 s/n, B1904AAN La Plata, Argentina.
KEYWORDS. Bio-based platform chemicals, Furanics, Dialkyl carbonates, Green chemistry,
ABSTRACT: Several alkyl carbonate derivatives of 5-hydroxymethylfurfural (HMF) and 2,5-bis(hydroxymethyl)furan (BHMF) have been synthesised for the first time. In most cases high
yields were achieved using mild reaction conditions and compounds were recovered as pure with none or minimal purification. The new HMF and BHMF derived products resulted stable over time and they are suitable monomers for new bio-based polycarbonates and polyurethanes.
INTRODUCTION
Biomass-derived C6-furanic platform chemicals are regarded as the most promising building blocks in biorefinery exploitation.1 5-Hydroxymethylfurfural (HMF) is referred as a “sleeping
giant” in consideration of its potential in bridging the gap from a fossil-based chemistry to a more sustainable one.2
A major advantage of HMF molecular structure is the absence of chiral centers, thus all C6-carbohydrates can be converted into this platform chemical, albeit with different selectivity.3
Furthermore, HMF is a versatile substrate with enormous market potential as it can be easily converted into high value chemicals, materials and bio-based polymers.1,4 However, there are
some limitations in developing a more efficient HMF-based chemistry, i.e., its preferred solubility in water, rather than organic solvents, the absence of a cost-efficient scale-up synthesis (HMF current price is 3900 €/kg)5 and its well know stability issue, partially solved by the
Figure 1. BHMF most investigated chemical transformation.
In this view, 2,5-bis(hydroxymethyl)furan (BHMF) is regarded as more stable bio-based platform chemical. Recent examples of industrially interesting BHMF chemical transformation include:
oxidation reactions leading to furan-2,5-dicarboxylic acid (FDCA) and 2,5-diformylfuran (DFF), used as monomers for polymers (PEF) and macrocycles;7
syntheses of bis(alkoxymethyl) furans (BAMF), potential fuel additives;8
preparation of bis(amino)furans (BAmMF)9 and bis(carbamate)furans (BCMF)10 regarded
as promising monomers for polymers;
easy access to bis(sulfonated) (BSMF)11 and bisacetyl (BAcMF)12 derivatives
investigated as monomers for polymers and bio-based acetylating agents respectively. Other interesting reactions include Diels-Alder cycloaddition leading to bis(hydroxymethyl)norcantharimide,13 cross coupling to form (monoester)methylhydroxyfuran
(MEHMF)14 and rearrangements reaction.15 BHMF scaffold has also being used for the
preparation of surfactants16 and pincers catalysts.17
In this work we exploited, the reactivity of HMF and BHMF with dialkyl carbonates (DACs)18
used as green solvents and reagents. To the best of our knowledge only two isolated examples have been reported in the literature exploring DAC-derivatives of furanics:
a lipase-catalyzed methoxy carbonylation of HMF via DMC where the so formed 5-(methoxycarbonyl)oxymethylfurfural (3) required the use of deep-eutectic solvents (DES) as separating agent;19
a reaction of BHMF with dipropylcarbonate and an excess of N,N-diisopropylethylamine (DIEA) as base leading to the related bis-alkylcarbonate product with a less than 10% isolated yield.20
Herein it is reported an easy synthetic approach to several alkyl carbonate derivatives of furanics employing mild reaction conditions; the high stability of the isolated new compounds render them suitable monomers for novel bio-based polycarbonates and polyurethanes, as well as, interesting reaction intermediates.
RESULTS AND DISCUSSION
HMF, used for this study, has been synthesized from D-fructose according to our recently reported procedure that employs acid catalyst Amberlyst-15 and dimethyl carbonate (DMC) as extracting solvent and avoids any purification technique.21
Alkoxycarbonylation of HMF was conducted by reaction of freshly prepared HMF with an excess of DMC (30 eq. mol) in the presence of potassium carbonate as base (1.0 eq. mol) at reflux temperature (#1; Table 1).
Table 1. HMF reactivity with DACsa
# K2CO3 DACs Na2S2O4 Temp. Yieldb
eq. mol (eq. mol) Weight % ° C %
1 1 DMC (30) - 90 1 41 2 - DMC (30) - 90 1 0c 3 1 DMC (30) - 60 1 13 4 1 DMC (30) 2 90 1 54 5 1 DEC (30) - 100 2 10c 6 1 DEC (30) - 140 2 16
a Reaction conditions: HMF (1.0 g) was freshly prepared19 and directly used for the preparation of the
alkyl carbonate derivatives 1-2. All reactions were conducted for 16 h; NMR analysis on the reaction mixture never showed the presence of residual HMF, thus conversion should be considered quantitative for all the experiments reported b Isolated yield; c After 5 hours NMR spectra showed that ca 20% of
HMF converted into humins; d Calculated via NMR.
The base was used to ensure deprotonation of the substrate hydroxyl moiety promoting the transesterification reaction. NMR analysis of the reaction mixture showed the presence of 5-(methoxycarbonyl)oxymethylfurfural 1 as the only product. The pure compound – in the form of low melting yellow crystals - was isolated by quick column chromatography on silica gel and its structure was confirmed by NMR spectra and high-resolution mass spectrometry.†
The moderate isolated yield of compound 1 (41%) is ascribable to a significant mass loss already evident in the recovered reaction mixture. Most probably the relatively high reaction temperature and the unstable nature of HMF led to humins formation at the same time of HMF methoxycarbonylation. This hypothesis was confirmed by repeating the reaction without the base (#2; Table 1). In this experiment the methylcarbonate derivative
1 was not formed, on the other hand decomposition of HMF was already visible after 5
The methoxycarbonylation reaction was then performed at 60 °C, to minimise HMF decomposition, however the isolated yield of compound 1 resulted only 13% (#3; Table 1). It can be deduced that at this temperature HMF alkoxycarbonylation is slower than the substrate decomposition taking simultaneously place.
The best result was achieved by performing the reaction at 90 °C in the presence of a small amount of sodium dithionite (#3; Table 1).6 Although at this temperature the
decomposition of the starting material is inevitable, sodium dithionite once again demonstrated its efficiency as HMF stabiliser. In fact, in this condition mass loss of the reaction mixture was reduced and the isolated yield increased up to 54%.
As expected, 5-(ethoxycarbonyl)oxymethylfurfural 2 was more difficult to isolate (#5-6; Table 1). Reaction conducted at 100 °C using diethyl carbonate (DEC) as solvent and reagent, resulted in 10% yield of compound 2, according to NMR spectrometry estimation (#4; Table 1). The ethyl carbonate derivative 2 was isolated as a pure compound via column chromatography in modest yield (16%) after performing the reaction at the refluxing temperature of DEC, 140 °C in the presence of 1.0 eq. mol of potassium carbonate (#5; Table 1).
From the mechanistic point of view, both alkyl carbonate derivatives 1 and 2 formed
according to a base-catalysed acylation mechanism (BAc2) under thermodynamic control
following the HSAB Person theory.22
The methoxycarbonyl compound 1 is an interesting intermediate as it encompasses two functional groups that can be easily modified or used as such. The product resulted very stable; NMR analysis performed over a period of a month did not show any evidence of its decomposition.
Several experiments have also been conducted to chemoselectively reduce the aldehyde group of methyl carbonate compound 1 to achieve
5-(hydroxymethyl)-2-(methoxycarbonyl)oxy methylfuran 3.†
Sodium borohydride was inefficient as the reducing agent, most probably as result of its basicity that might promote transesterification reaction of the compound 3, once formed. An experiment was also performed by using Pd/C catalyst in the presence of hydrogen. The reaction led to a complex mixture of compounds; attempted column chromatography was not successful in recovering the compound 3. Investigation on more selective reducing catalysts is currently ongoing.
The reactivity of more stable BHMF with several DACs - via BAC2 mechanism - was
next investigated (#1-8; Table 2). All experiments were conducted by reacting BHMF (0.5 grams) with an excess of the selected DAC (6-30 eq. mol) in the presence of potassium carbonate (2.0 eq. mol) as a base.
DACs, used as reagents and solvents, can be, in most cases, recovered at the end of the reaction by distillation and eventually reused. Due to its cheap price and easy availability, recycling of K2CO3 was not herein investigated.
Scheme 2. Reactivity of BHMF with organic carbonates.
A preliminary experiment was conducted reacting BHMF and an excess of DMC in the absence of base (#1; Table 2). The substrate resulted partially insoluble in DMC and, after six hours at reflux temperature, showed a low conversion (15%) into the
monomethylcarbonate derivative 3 (100% selectivity). Conversely,
2,5-bis[(methoxycarbonyl)oxymethyl]furan 4 and 2,5-bis[(ethoxycarbonyl)oxymethyl]furan 5 were readily synthesized in high yields (87 and 76% respectively) using commercially available DMC and DEC (#2-3; Table 2) in the presence of potassium carbonate. These results demonstrated that the base not only promoted the alkoxycarbonylation reaction, but also improved solubility of BHMF in the DAC.
Table 2. BHMF reactivity with DACsa
# ROCOOR K2CO3 Temp. Time Conv.b Yieldc
R= (eq. mol) (eq. mol) ° C h % %
1d CH 3 (30) - 90 6 15 3 15b 2 CH3 (30) 2.0 90 6 100 4 87 3 CH2CH3 (30) 2.0 140 6 100 5 76 4 CH2CH=CH2 (10) 2.0 140 6 100 6 70 5 CH2CH2OCH3 (10) 2.0 100 24 70e 7 26 6 (CH2CH2O)2OCH3 (6) 2.0 100 24 40 8 10 7 CH2Ph (6) 2.0 100 24 40 9 20c 8 Ph (6) 2.0 100 24 100 10 nd 9f CH 3 (5) 1.0 90 6 80g 3 13c 10h CH 3 (5) 1.0 60 6 50i 3 25 11 CH3 (3) 1.0 60 6 45j 3 20
a Reaction conditions: BHMF 0.5 gr in the presence of 2.0 eq. mol of K
2CO3; b BHMF conversion was
evaluated via 1H NMR spectroscopy; c Isolated yield; d Reaction conducted in the absence of base; e
Selectivity calculated via NMR showed 70% of the product 7 and 30% of the monocarbonate derivative; f
Reaction conditions: BHMF (0.5 g), 1.0 eq. mol of K2CO3 in 100 mL of CH3CN; g Selectivity calculated
via NMR showed 16% of monocarbonate compound 3 and 84% of compound 4; h Reaction conditions:
BHMF (0.5 g) 1.0 eq. mol of K2CO3 in 6 mL of MeTHF; i Selectivity calculated via NMR showed 90% 3
and 10% of 4; j Selectivity calculated via NMR showed 85% 3 and 15% of 4
The bis(methyl carbonate) derivative 4 was isolated as a light yellow solid, meanwhile the bis(ethyl carbonate) compound 5 was a brownish oil. Both compounds were fully characterised and showed high stability over time. The easy synthetic procedure to bis(alkyl carbonate) compounds 4-5 renders them interesting monomers for polycarbonates and polyurethanes derived from BHMF that are so far only scarcely investigated.23
The alkoxycarbonylation reaction was also conducted by employing commercially available diallyl carbonate. 2,5-Bis[(allyloxycarbonyl)oxymethyl]furan 6 was isolated in high yield (#4; Table 2) after filtering the exhausted base from the reaction mixture and distillation of the exceeding DAC under vacuum. The presence of the double bond in the structure of the monomer 6 opens up the possibility to numerous further derivatisations
such as i) sulfonation reaction leading to new surfactants, ii) epoxidation of the double bond leading to monomers for polymers, iii) preparation of organosilsesquioxanes to be used in sol-gel chemistry, etc. Preliminary investigations on similar allyl derivatives of
C6 sugar-based monomers, such as isosorbide, have already been reported.24
Furthermore, the bis(allyl carbonate) derivative 6 could be used as monomer for the preparation of polymers via photoirradiation or employing Grubbs catalysts.25
Samples of bis(2-methoxyethyl) carbonate and bis(2-(2-methoxyethoxy)ethyl) carbonate available in our laboratory were used to attempt the synthesis of the related bis(alkyl carbonate) derivatives 7-8 (#5-6; Table 2).
2,5-Bis[(2-methoxyethoxycarbonyl)oxymethyl]furan 7 was isolated only in modest yield (26 %) as a brownish oil after distillation of the exceeding DAC.
In the case of compound 8 the yield was even lower as a result of the more sterically hindered carbonyl group of the starting DAC and its high boiling point that rendered the purification via distillation quite complicated.
Similar difficulties were encountered also in the experiment conducted with dibenzyl carbonate (#7; Table 2). The desired product 9 was identified via NMR analysis, however in the investigated reaction conditions, BHMF conversion was only moderate and purification could eventually be achieved only via column chromatography.
An experiment (#8; Table 2) was carried out employing commercially available diphenyl carbonate (DPC). The high reactivity of DPC as carbonylating agent led to a mixture of products including small oligomers, thus the synthesis of the related bis(phenyl carbonate) derivative 10 was no further investigated at this stage.
Some preliminary investigations were then conducted for the preparation of the monomethoxycarbonyl derivative 3. In this case, BHMF was reacted with DMC (5.0 eq. mol) in CH3CN (100 mL) using potassium carbonate (1.0 eq. mol) as a base. High
dilution was used in order to minimize the formation of the bis(methyl carbonate) derivative 4 (#9; Table 2).
In these conditions, small amount of product 3 was detected in the reaction mixture and column chromatography was attempted to achieve a sample of the desired product. Interestingly, NMR spectrum of the purest fraction isolated showed – together with compound 3 - presence of another product with a very symmetrical structure (only two
peaks according to proton NMR spectrum).† It was speculated that due to the diluted
reaction conditions (BHMF 0.04 mol/L), a small amount of the 8-membered cyclic carbonate 11 was formed via an intramolecular BAc2 reaction of the mono(methyl
carbonate) derivative 3 (Scheme 3).
Scheme 3. Formation of 8-membered cyclic carbonate 11 from BHMF.
A sample of the cyclic carbonate 11 was thus synthesised by reaction of BHMF with 1,1′-carbonyldiimidazole (CDI) using potassium carbonate as a base in diluted conditions. The purification of the product was rather complicated by the presence of
excess imidazole released as leaving group during the cyclisation reaction. The pure cyclic carbonate could be finally isolated either by numerous washing of the reaction mixture with a diethyl ether/ethyl acetate solution or via column chromatography. Full characterisation of compound 11 confirmed the proposed structure, as well as, its presence as by-product in the attempted synthesis of compound 3 (#9, Table 2).†
The cyclic carbonate 11 would be a very interesting monomer for polycarbonate preparation; further experiments on this compound are on-going.
The synthesis of 5-(hydroxymethyl)-2-(methoxycarbonyl) oxymethylfuran 3 was then carried out using a less polar solvent, i.e. 2-methyltetrahydrofuran, more concentrated reaction conditions (BHMF 0.66 mol/L) and lower temperature (#10; Table 2). In these conditions the product 3 was isolated as pure in modest yield (25%) after column chromatography. Bis(methyl carbonate) derivative 4 and residual starting material were also detected in the reaction mixture. An experiment conducted decreasing the amount of DMC, resulted in a similar isolated yield of compound 3 (#11, Table 2). Further studies on this monomer will be carried out focussing on optimizing the reaction conditions.
A synthetic procedure to bis(alky carbonate) furanics is herein reported for the first time by reaction of HMF or BHMF with selected DACs in the presence of potassium carbonate as a base in mild conditions.
5-(Methoxycarbonyl)oxy methylfurfural 1 was achieved in good yield upon reacting HMF with DMC; the pure compound was isolated after minimal purification. This product incorporates two reactive groups that can be further functionalised and possess high stability over time.
A series of bis(alkyl carbonate) derivatives of BHMF was then prepared via DAC chemistry employing potassium carbonate as a base. Commercially available DMC, DEC and diallyl carbonate led to the related BHMF derivatives 4-6 in very good yield (70-87%). The products were isolated by filtration of the exhausted base and distillation of the exceeding DAC without any further purification. These compounds have numerous potentials as monomers for bio-based polycarbonates or polyurethanes, as well as, starting materials for surfactants and detergents.
Sterically more hindered DACs, i.e., bis(2-methoxyethyl) carbonate, bis(2-(2-methoxyethoxy)ethyl)carbonate, dibenzyl carbonate and diphenyl carbonate required either harsh reaction conditions or purification of the products via column chromatography.
Noteworthy, this study also led to the isolation of BHMF mono(methyl carbonate) derivative 3 and a 8-membered cyclic carbonate 11. These compounds have been isolated in modest yield and fully characterized. Their potential application as monomer for polymers such as polycarbonates is evident, optimization and implementation of their preparation is currently on-going.
ASSOCIATED CONTENT
Supporting Information.† Supplementary Information (SI) available includes experimental
procedure and complete characterization of compounds 1-11 (NMR spectra and exact mass). AUTHOR INFORMATION
Corresponding Author
*Fabio Aricò: [email protected]
ACKNOWLEDGEMENTS
This work was financially supported by the Organization for the Prohibition of Chemical Weapons (OPCW); Project Number L/ICA/ICB/218789/19. Dr. Angel Gabriel Sathicq was financed by OPCW Fellowship program. Dr. Iskandar Abdullah was financed by Erasmus+ ICM KA107 grant.
REFERENCES
1. a) 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 (4), 539-554. DOI: 10.1039/B922014C; b) Kucherov, K. A.; Romashov, L. V.; Galkin, K. I.; Ananikov, V. P. Chemical Transformations of Biomass-Derived C6-Furanic Platform Chemicals for Sustainable Energy Research, Materials Science, and Synthetic Building Blocks. ACS Sustainable Chem. Eng., 2018, 6, 8064-8092. DOI: 10.1021/acssuschemeng.8b00971.
2. Galkin, K. I; Ananikov, V. P. When Will 5 Hydroxymethylfurfural, the “Sleeping Giant”‐ of Sustainable Chemistry, Awaken? ChemSusChem, 2019, 12, 2976-2982. DOI: 10.1002/cssc.201900592
3. a) 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 (3), 1499-1597.DOI:10.1021/cr300182k; b) Mika, L. T.; Cséfalvay, E.; Németh, Á., Catalytic Conversion of Carbohydrates to Initial Platform Chemicals: Chemistry and Sustainability. Chem. Rev., 2018, 118 (2), 505-613. DOI: 10.1021/acs.chemrev.7b00395; c) Zhao, D.; Rodriguez-Padron, D.; Luque, R.; Len, C., Insights into the Selective Oxidation of 5-Hydroxymethylfurfural to 5-Hydroxymethyl-2-furancarboxylic Acid Using Silver Oxide. ACS Sustainable Chem. Eng. 2020, 8 (23), 8486–8495. DOI: https://doi.org/10.1021/acssuschemeng.9b07170
4. Kong, X.; Zhu, Y.; Fang, Z.; Kozinski, J. A.; Butler, I. S.; Xu, L.; Song, H.; Wei, X. Catalytic conversion of 5-hydroxymethylfurfural to some value-added derivatives. Green
Chem., 2018, 20, 3657-3682. DOI: 10.1039/C8GC00234G.
5. Price according to Sigma Aldrich catalogue.
6. Gomes, R. F. A.; Mitrev, Y. N.; Simeonov, S. P.; Afonso, C. A. M., Going Beyond the Limits of the Biorenewable Platform: Sodium Dithionite-Promoted Stabilization of
5-Hydroxymethylfurfural. ChemSusChem, 2018, 11 (10), 1612-1616. DOI:
10.1002/cssc.201800297
7. a) Kokoh, K. B.; Belgsir, E. M. Electrosynthesis of furan-2,5-dicarbaldehyde by programmed potential electrolysis. Tetrahedron Lett., 2002, 43, 229-231. DOI: 10.1016/S0040-4039(01)02106-2; b) Chatterjee, M.; Ishizaka, T.; Chatterjeeb, A.; Kawanami, H. Dehydrogenation of 5-hydroxymethylfurfural to diformylfuran in compressed carbon dioxide: an oxidant free approach. Green Chem., 2017, 19, 1315-1326. DOI: 10.1039/C6GC02977A; c) Han, G.; Jin, Y.-H.; Burgess, R. A.; Dickenson, N. E.; Cao, X.-M.; Sun, Y. Visible-Light-Driven Valorization of Biomass Intermediates Integrated with H2 Production Catalyzed by Ultrathin Ni/CdS Nanosheets. J. Am. Chem. Soc., 2017, 139, 15584-15587. DOI: 10.1021/jacs.7b08657.
8. a) Musolino, M.; Ginès-Molina, M. J.; Moreno-Tost, R.; Aricò, F. Purolite-Catalyzed Etherification of 2,5-Bis(hydroxymethyl)furan: A Systematic Study. ACS Sustainable
Chem. Eng., 2019, 7, 10221-10226; b) Cao, Q.; Liang, W.; Guan, J.; Wang, L.; Qu, Q.;
(5), 49-53. DOI: 10.1016/j.apcata.2014.05.003; c) Sacia, E. R.; Balakrishnan, M.; Bell, A. T., Biomass conversion to diesel via the etherification of furanyl alcohols catalyzed by Amberlyst-15. J. Catal., 2014, 313, 70-79. DOI: 10.1016/j.jcat.2014.02.012; d) Gupta, D.; Saha. B. Dual acidic titania carbocatalyst for cascade reaction of sugar to etherified fuel additives. Catal. Commun. 2018, 110, 46-50; e) Balakrishnan, M.; Sacia, E. R.; Bell, A. T., Etherification and reductive etherification of (hydroxymethyl)furfural: 5-(alkoxymethyl)furfurals and 2,5-bis(alkoxymethyl)furans as potential bio-diesel candidates. Green Chem. 2012, 14 (6), 1626-1634. DOI: 10.1039/C2GC35102A.; f) Hu, H.; Hu, D.; Jin, H.; Zhang, P.; Li, G.; Zhou, H.; Yang, Y.; Chen, C.; Zhang, J.; Wang, L.; Efficient Production of Furanic Diether in a Continuous Fixed Bed Reactor.
ChemCatChem, 2019, 11, 2179-2186. DOI: 10.1002/cctc.201900054; g) Jae, J.;
Mahmoud, E.; Lobo, R. F.; Vlachos, D. G. Cascade of Liquid Phase Catalytic Transfer‐ Hydrogenation and Etherification of 5 Hydroxymethylfurfural to Potential Biodiesel‐ Components over Lewis Acid Zeolites. ChemCatChem, 2014, 6, 508-513. DOI: 10.1002/cctc.201300978; h) Han, J.; Kim, Y.-H.; Junga, B. Y.; Hwang, S. Y.; Jegal, J.; Kim, J. W.; Lee, Y.-S. Highly Selective Catalytic Hydrogenation and Etherification of 5-Hydroxymethyl-2-furaldehyde to 2,5-Bis(alkoxymethyl)furans for Potential Biodiesel Production. Synlett, 2017, 28, 2299-2302. DOI: 10.1055/s-0036-1589076; i) Stensrud, K.; Venkitasubramanian, P. Ma, C.-C. CO2-mediated Etherification of Bio-based diols
WO2016/99789, 2016.
9. a) Pingen, D.; Schwaderer, J. B.; Walter, J.; Wen, J.; Murray, G.; Vogt D.; Mecking, S. Diamines for Polymer Materials via Direct Amination of Lipid and Lignocellulose based‐ ‐
10.1002/cctc.201800365; b) Li, P.; Liebens A. T. A process for producing a tetrahydrofuran compound comprising at least two amine functional group. WO2018/113599, 2018.
10. Stensrud, K. Synthesis of dicarbamates from reduction products of 2-hydroxymethyl-5-furfural (HMF) and derivatives thereof WO2014/200636A1, 2015.
11. Stensrud, K. Sulfonates of Furan-2,5-dimethanol and (tetrahydrofuran-2,5-diyl)dimethanol and derivatives thereof. WO2015/94965, 2015.
12. De, S.; Kumar, T.; Bohre, A.; Singh, L. R.; Saha, B. Furan-based acetylating agent for the chemical modification of proteins. Bioorg. Med. Chem., 2015, 23, 791-796. DOI: 10.1016/j.bmc.2014.12.053.
13. Kucherov, F. A.; Galkin, K. I.; Gordeev, E. G.; Ananikov, V. P. Efficient route for the construction of polycyclic systems from bioderived HMF. Green Chem., 2017, 19, 4858-4864. DOI: 10.1039/C7GC02211E.
14. Cheng, J.; Zhu, M.; Wang, C.; Li, J.; Jiang, X.; Wei, Y.; Tang, W.; Xuea, D.; Xiao, J. Chemoselective dehydrogenative esterification of aldehydes and alcohols with a dimeric rhodium(ii) catalyst. Chem. Sci., 2016, 7, 4428-4434. DOI: 10.1039/C6SC00145A. 15. Falenczyk, C.; Pölloth, B.; Hilgers, P.; König, B. Mechanochemically Initiated
Achmatowicz Rearrangement. Synth. Commun., 2015, 45, 348-354. DOI: 10.1080/00397911.2014.963624
16. Kipshagen, L.; Vömel, L. T.; Liauw, M. A.; Klemmer, A.; Schulz, A.; Kropf, C.; Hausoul P. J. C.; Palkovits, R. Anionic surfactants based on intermediates of carbohydrate conversion. Green Chem., 2019, 21, 3882-3890. DOI: 10.1039/C9GC01163C.
17. Haibach, M. C.; Wang, D. Y.; Emge, T. J.; Krogh-Jespersen K.; Goldman, A. S. (POP)Rh pincer hydride complexes: unusual reactivity and selectivity in oxidative addition and olefin insertion reactions. Chem. Sci., 2013, 4, 3683-3692.
18. Tundo, P.; Musolino, M.; Aricò, F. The reactions of dimethyl carbonate and its derivatives. Green Chem., 2018, 20, 28-85. DOI: 10.1039/c7gc01764b.
19. Krystof, M.; Pèrez-Sànchez, M.; Domìnguez de Maria, P. Lipase Catalyzed‐ (Trans)esterification of 5 Hydroxy methylfurfural and Separation from HMF Esters‐ ‐
using Deep Eutectic Solvents. ‐ ChemSusChem, 2013, 6, 630-634. DOI:
10.1002/cssc.201200931
20. Stensrud, K.; Venkitasub-Ramaniam, P. Direct synthesis of bio-based alkyl & furanic diol ethers , acetates, ether-acetates and corbonates. WO 2015/095710 A, 2015.
21. Musolino, M.; Andraos, J.; Aricò, F. An Easy Scalable Approach to HMF Employing DMC as Reaction Media: Reaction Optimization and Comparative Environmental Assessment. ChemistrySelect, 2018, 2, 2359-2365. DOI:10.1002/slct.201800198.
22. Pearson, R. G. Hard and Soft Acids and Bases. J. Am. Chem. Soc., 1963, 85, 3533-3539. DOI: 10.1021/ja00905a001.
23. a) Choi, E. H.; Lee, J.; Son, S. U.; Song, C. Biomass derived furanic polycarbonates:‐ Mild synthesis and control of the glass transition temperature. J. Polymer Science A:
Polym. Chem., 2019, 57, 1796-1800. DOI: 10.1002/pola.29448; b) Zhang, L.; Michel Jr,
F. C.; Co, A. C. Nonisocyanate route to 2,5 bis(hydroxymethyl)furan based‐ ‐ polyurethanes crosslinked by reversible diels–alder reactions. J. Polymer Science A:
Polym. Chem., 2019, 57, 1495-1499. DOI: 10.1002/pola.29418.
24. a) Cho, J.-E.; Sim, D.-S.; Kim, Y.-W.; Lim, J.; Jeong N.-H.; Kang, H.-C. Selective Syntheses and Properties of Anionic Surfactants Derived from Isosorbide. J. Surfact.
Deterg., 2018, 21, 817-826. DOI: 10.1002/jsde.12182; b) Versace, D.-L.; Cerezo Bastida,
J.; Lorenzini, C.; Cachet-Vivier, C.; Renard, E.; Langlois, V.; Malval P.; Fouassier, J.-P.; Lalevée, J. A Tris(triphenylphosphine)ruthenium(II) Complex as a UV Photoinitiator for Free-Radical Polymerization and in Situ Silver Nanoparticle Formation in Cationic Films. Macromolecules, 2013, 46, 8808-8815. DOI: 10.1021/ma4019872; c) Lorenzini, C.; Versace, D. L.; Gaillet, C.; Lorthioir, C.; Boileau, S.; Renard, E.; Langlois, V. Hybrid networks derived from isosorbide by means of thiol-ene photoaddition and sol–gel chemistry. Polymer, 2014, 55, 4432-4440. DOI: 10.1016/j.polymer.2014.06.077
25. a) Lorenzini, C.; Haider, A.; Kang, I.-K.; Sangermano, M.; Abbad-Andalloussi, S.; Mazeran, P.-E.; Lalevée, J.; Renard, E.; Langlois, V.; Versace, D.-L. Photoinduced Development of Antibacterial Materials Derived from Isosorbide Moiety.
Biomacromolecules, 2015, 16, 683-694. DOI: 10.1021/bm501755r. b) Ogba, O. M.;
Warner, N. C.; O'Leary, D. J.; Grubbs, R. H. Recent advances in ruthenium-based olefin metathesis. Chem. Soc. Rev., 2018, 47, 4510-4544. DOI: 10.1039/C8CS00027A.
SYNOPSIS
The reaction of platform chemicals HMF/BHMF with dialkyl carbonates, used as green solvent and reagent, led to a new family of bio-based stable compounds.
TOC/Abstract Graphic
