Non-catalytic synthesis of Chromogen I and III from N-acetyl-d-glucosamine in high-temperature water

Osada, Motonobu; Kikuta, Kazushi; Yoshida, Kohei; Totani, Kiichiro; Ogata, Makoto; Usui, Taichi

doi:10.1039/c3gc41161c

Cited by 75 publications

(54 citation statements)

References 27 publications

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“…Besides, other dehydration products such as Chromogen I, Chromogen III, 2-acetamido-3,6-anhydro-2-deoxy-D-glucofuranose (3,6-anhydro-GNF) and 2-acetamido-3,6-anhydro-2-deoxy-D-mannofuranose (3,6-anhydro-MNF) were formed by the alkali treatment of NAG [36], or incubation in a borate solution [37]. Very recently, non-catalytic dehydration of NAG into Chromogen I and III was achieved in the absence of additives in high-temperature pure water [38]. The kinetic modelling indicated that the formation of Chromogen I is favored by lower temperature and Chromogen III preferentially forms at higher temperatures, at a time scale of seconds.…”

Section: Conversion Of Chitin Monomermentioning

confidence: 99%

Novel Catalytic Systems to Convert Chitin and Lignin into Valuable Chemicals

Chen

Yan

2014

Catal Surv Asia

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This review briefs the emerging strategies for the designing of catalysts and catalytic systems to upgrade waste biomass into value-added chemicals, with an emphasis on the efforts and advances in our group. The review covers the valorization of chitin and lignin materials, which are most abundant N-containing and the most abundant aromatic polymers, respectively. In the chitin part, we show case existing examples on chitin monomer and chitin transformation into renewable, N-containing chemicals. Oxidation, hydrolysis, dehydration reactions will be introduced. In lignin part we mainly introduce novel catalyst for lignin hydrogenolysis, in particular Ni based monometallic and bimetallic catalysts. The structure-activity correlations will be discussed in detail. We finally describe some of the undergoing works in the group and highlight a few potential directions worth investigation in the future.

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Section: Conversion Of Chitin Monomermentioning

confidence: 99%

Novel Catalytic Systems to Convert Chitin and Lignin into Valuable Chemicals

Chen

Yan

2014

Catal Surv Asia

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“…Interestingly, the decomposition rate of GlcNAc is greater than that of glucose (Osada et al 2013a), which is opposite trend between α-chitin and cellulose. For GlcNAc, the dehydration proceeds between H-2 and OH-3 because the N-acetyl group is an electron-withdrawing group and the elimination of H-2 takes place easier, as compared with glucose.…”

Section: Effects Of Sub-and Supercritical Water Treatments On the Promentioning

confidence: 99%

Effect of sub- and supercritical water treatments on the physicochemical properties of crab shell chitin and its enzymatic degradation

Osada

Miura

Nakagawa

et al. 2015

Carbohydrate Polymers

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This study examined the effects of sub-and supercritical water pretreatments on the physicochemical properties of crab shell α-chitin and its enzymatic degradation to obtain N,N'-diacetylchitobiose (GlcNAc)2. Following sub-and supercritical water pretreatments, the protein in the crab shell was removed and the residue of crab shell contained α-chitin and CaCO3. Prolonged pretreatment led to α-chitin decomposition. The reaction of pure α-chitin in sub-and supercritical water pretreatments was investigated separately; we observed lower mean molecular weight and weaker hydrogen bonds compared with untreated α-chitin.(GlcNAc)2 yields from enzymatic degradation of subcritical (350C, 7 min) and supercritical water (400C, 2.5 min) pretreated crab shell were 8% and 6%, compared with 0% without any pretreatment. This study shows that sub-and supercritical water pretreatments of crab shell provide to an alternative method to the use of acid and base for decalcification and deproteinization of crab shell required for (GlcNAc)2 production.

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“…[3] Nacetyl-d-glucosamine (NAG) is the monomer of chitin, and can be converted into a N-containing product, 3-acetamido-5-acetylfuran (3A5AF), through dehydration (Scheme 1). [8] As an alternative to dehydrative approaches to using this renewable aminosugar, the aerobic oxidation of NAG has been performed in water by using gold nanoparticle catalysts to give N-acetylglucosaminic acid. Previously, 3A5AF was obtained from NAG by use of pyrolysis methods, but the yields were very low (2 % and 0.04 %).…”

Section: Introductionmentioning

confidence: 99%

“…[7] NAG has also been partially dehydrated in superheated water under autocatalytic conditions to yield Chromogen I and Chromogen III in yields of 23 %. [8] As an alternative to dehydrative approaches to using this renewable aminosugar, the aerobic oxidation of NAG has been performed in water by using gold nanoparticle catalysts to give N-acetylglucosaminic acid. [9] To date, no studies on the chemistry of 3A5AF beyond its preparation have been reported, so this compound is awaiting further exploration in terms of its physical and chemical properties.…”

Section: Introductionmentioning

confidence: 99%

Combined Experimental and Computational Studies on the Physical and Chemical Properties of the Renewable Amide, 3‐Acetamido‐5‐acetylfuran

2014

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The pK(a) of 3-acetamido-5-acetylfuran (3A5AF) was predicted to be in the range 18.5-21.5 by using the B3LYP/6-311+G(2d,p) method and several amides as references. The experimental pK(a) value, 20.7, was determined through UV/Vis titrations. Its solubility was measured in methanol-modified supercritical CO2 (mole fraction, 3.23×10(-4), cloud points 40-80 °C) and it was shown to be less soluble than 5-hydroxymethylfurfural (5-HMF). Dimerization energies were calculated for 3A5AF and 5-HMF to compare hydrogen bonding, as such interactions will affect their solubility. Infrared and (1) H nuclear magnetic resonance spectra of 3A5AF samples support the existence of intermolecular hydrogen bonding. The highest occupied molecular orbital, lowest unoccupied molecular orbital, and electrostatic potential of 3A5AF were determined through molecular orbital calculations using B3LYP/6-311+G(2d,p). The π-π* transition energy (time-dependent density functional theory study) was compared with UV/Vis data. Calculated atomic charges were used in an attempt to predict the reactivity of 3A5AF. A reaction between 3A5AF and CH3MgBr was conducted. As 3A5AF is a recently developed renewable compound that has previously not been studied extensively, these studies will be helpful in designing future reactions and processes involving this molecule.

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Non-catalytic synthesis of Chromogen I and III from N-acetyl-d-glucosamine in high-temperature water

Cited by 75 publications

References 27 publications

Novel Catalytic Systems to Convert Chitin and Lignin into Valuable Chemicals

Novel Catalytic Systems to Convert Chitin and Lignin into Valuable Chemicals

Effect of sub- and supercritical water treatments on the physicochemical properties of crab shell chitin and its enzymatic degradation

Combined Experimental and Computational Studies on the Physical and Chemical Properties of the Renewable Amide, 3‐Acetamido‐5‐acetylfuran

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