Stable complex formation with boric acid in pyrolysis of levoglucosan in acidic media

Kawamoto, Hiroyuki; Saka, Shiro

doi:10.1016/j.jaap.2007.12.008

Cited by 10 publications

(5 citation statements)

References 21 publications

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“…14 We assessed the ability of twenty derivatives of phenylboronic acid to promote the conversion of glucose to HMF (Tables S2–S4 in the Supporting Information). Our data corroborated the earlier work with phenylboronic acid itself, 15 which is not a catalyst in our hands, but revealed that adding an ortho carboxyl group engenders catalysis, especially in the presence of MgCl 2 ·6H 2 O (Table 1). Further optimization revealed prospects for catalytic turnover.…”

Section: Resultssupporting

confidence: 92%

“…The precedents were discouraging, however, as phenylboronic acid had been reported to inhibit the hydrolysis of cellulose and the dehydration of sugar monomers. 15,16 …”

Section: Resultsmentioning

confidence: 99%

“…The precedents were discouraging, however, as phenylboronic acid had been reported to inhibit the hydrolysis of cellulose and the dehydration of sugar monomers. 15,16 Phenylboronic acids have an affinity for carbohydrates that is tunable based on substituents. 14 We assessed the ability of twenty derivatives of phenylboronic acid to promote the conversion of glucose to HMF (Tables S2-S4 in the ESI †).…”

Section: Resultsmentioning

confidence: 99%

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Organocatalytic conversion of cellulose into a platform chemical

2013

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The search for a source of fuels and chemicals that is both abundant and renewable has become of paramount importance. The polysaccharide cellulose meets both criteria, and methods have been developed for its transformation into the platform chemical 5-(hydroxymethyl)furfural (HMF). These methods employ harsh reaction conditions or toxic heavy metal catalysts, deterring large-scale implementation. Here, we describe a low-temperature, one-pot route that uses ortho-carboxyl-substituted phenylboronic acids as organocatalysts in conjunction with hydrated magnesium chloride and mineral acids to convert cellulose and cellulose-rich municipal waste to HMF in yields comparable to processes that use toxic heavy metal catalysts. Isotopic labeling studies indicate that the key aldose-to-ketose transformation occurs via an enediol intermediate. The route, which also allows for facile catalyst recovery and recycling, provides a green prototype for cellulose conversion.

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Section: Resultssupporting

confidence: 92%

“…The precedents were discouraging, however, as phenylboronic acid had been reported to inhibit the hydrolysis of cellulose and the dehydration of sugar monomers. 15,16 …”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Organocatalytic conversion of cellulose into a platform chemical

2013

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“…This is perhaps a result of the formation of a stable 2,3,4,6‐diphenylboronicfructose complex, as 2 b has a stronger binding constant for fructose (4400 mol −1 ) than for glucose (110 mol −1 ) 9a. The observation that phenylboronic acid itself inhibits sugar conversion into HMF has been reported previously by Kawamoto et al 9b…”

Section: Methodssupporting

confidence: 59%

Acidic Ionic Liquids as Sustainable Approach of Cellulose and Lignocellulosic Biomass Conversion without Additional Catalysts

2015

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The use of ionic liquids (ILs) for biomass processing has attracted considerable attention recently as it provides distinct features for pre-treated biomass and fractionated materials in comparison to conventional processes. Process intensification through integration of dissolution, fractionation, hydrolysis and/or conversion in one pot should be accomplished to maximise economic and technological feasibility. The possibility of using alternative ILs capable not only of dissolving and deconstructing selectively biomass but also of catalysing reactions simultaneously are a potential solution of this problem. In this Review a critical overview of the state of the art and perspectives of the hydrolysis and conversion of cellulose and lignocellulosic biomass using acidic ILs using no additional catalyst are provided. The efficiency of the process is mainly considered with regard to the hydrolysis and conversion yields obtained and the selectivity of each reaction. The process conditions can be easily tuned to obtain sugars and/or platform chemicals, such as furans and organic acids. On the other hand, product recovery from the IL and its purity are the main challenges for the acceptance of this technology as a feasible alternative to conventional processes.

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“…Accordingly, levoglucosenone and 5-HMF/furfural can be prepared selectively by bubbling nitrogen under a mild vacuum condition and steam injection, respectively. Addition of boric acid to this stem inhibits these dehydration reactions by the formation of stable complex with boric acid [131], which also stabilizes cellulose against depolymerization even in the presence of sulfuric acid [132]. γ-Lactone 5 was reported for the first time in 1988 by Furneaux et al [133] from the pyrolyzates of cellulose in the presence of Lewis acids.…”

Section: Dehydrationmentioning

confidence: 99%

Review of Reactions and Molecular Mechanisms in Cellulose Pyrolysis

Kawamoto

2016

COC

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Cellulose, which is a polymer of β-1→4 linked D-glucose units, comprises about half the components of lignocellulosic biomasses. A better understanding of the chemistry involved in cellulose pyrolysis provides valuable insights into the development of efficient pyrolysis-based conversion technologies of biomass into biofuels, biochemicals and biomaterials. This review focuses on the reactions and molecular mechanisms that determine the reactivity and product selectivity in pyrolysis and the related conversion technologies. This information is useful for understanding the processing technologies conducted at high temperatures, such as wood drying and the production of cellulose-plastic composite materials. Because the cellulose pyrolysis behavior changes drastically in the temperature range of 300-350 °C, this review is divided into low-and high-temperature regimes. The intermediates produced from cellulose pyrolysis are further converted into various gas, liquid or solid products. Hence, these processes are addressed as primary pyrolysis and secondary reactions in this review. The roles of the crystalline cellulose in pyrolysis are noted.

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Stable complex formation with boric acid in pyrolysis of levoglucosan in acidic media

Cited by 10 publications

References 21 publications

Organocatalytic conversion of cellulose into a platform chemical

Organocatalytic conversion of cellulose into a platform chemical

Acidic Ionic Liquids as Sustainable Approach of Cellulose and Lignocellulosic Biomass Conversion without Additional Catalysts

Review of Reactions and Molecular Mechanisms in Cellulose Pyrolysis

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