Oxidation of D-Galactose and Cellulose with Nitric Acid, Nitrous Acid and Nitrogen Oxides

Pigman, Ward; Browning, B. L.; McPherson, W. H.; Calkins, Chris R.; Leaf, R. L.

doi:10.1021/ja01174a076

Cited by 28 publications

(10 citation statements)

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“…25 Noticeably, marine-based carbohydrates contain galactose-type monosaccharides such as agarose, while land-based carbohydrates consist of glucose-type monosaccharides such as starch and cellulose. Unlike glucose, galactose is oxidized to the optically inactive galactaric acid (Gal-dA, trivially called mucic acid), and galactaric acid precipitates during oxidation with nitric acid due to its low solubility in water; 26 therefore, it can be readily isolated and employed as a starting material for various valueadded chemicals. Furan-2,5-dicarboxylic acid (2,5-FDCA) is a natural di-acid found inside the human body and was prominently named among the top 12 priority biobased molecules for the future "green" industry by the U.S. Department of Energy.…”

Section: ■ Introductionmentioning

confidence: 99%

Furan-2,5- and Furan-2,3-dicarboxylate Esters Derived from Marine Biomass as Plasticizers for Poly(vinyl chloride)

et al. 2019

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Esters of furan dicarboxylic acids (DAFs) were synthesized by a one-pot reaction between marine biomass-derived galactaric acid and bioalcohol under solvent-free conditions and were fully characterized. The catalyst amount could be reduced without loss of reaction yields using pxylene as the material separation agent. Also, a possible mechanism was proposed for the first time. Then the properties of four DAFs as plasticizers on the poly(vinyl chloride) (PVC) matrix were investigated. The experimental results showed that DAFs exhibit competitive efficiencies of plasticization when compared to the most commercialized plasticizer, DOP. It was found that the combination of DAFs and PVC produced homogeneous smooth-surface films, indicating miscibility between them. ATR-FTIR depicted the upshift of carbonyl absorption bands after mixing with the PVC matrix, with a magnitude of at most 18−21 cm −1 . TGA, DSC, and UTM data illustrated equivalent plasticization efficiencies. Due to their small molecular weights, the investigated DAFs are more volatile. However, due to bearing an oxygen atom in the aromatic furan ring, the degree of polarization of DAFs was boosted and helped inhibit leaching into the surrounding media. In brief, these synthetic compounds have promising feasibility as biobased plasticizers. Moreover, another interesting point is that the properties of furan-2,3-dicarboxylic acid derivatives were studied for the first time and herein reported.

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Section: ■ Introductionmentioning

confidence: 99%

Furan-2,5- and Furan-2,3-dicarboxylate Esters Derived from Marine Biomass as Plasticizers for Poly(vinyl chloride)

et al. 2019

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“…Non-selective oxidation of cellulose can be performed in a wide variety of oxidative systems, in the presence of nitrogen oxides [ 75 , 76 ], nitrates and nitrites [ 77 ], peroxides [ 78 ], sodium chlorite [ 79 ], permanganates [ 80 , 81 ], and even ozone [ 82 , 83 ] or lead (IV) tetraacetate [ 77 ] as non-specific oxidants. Most of these reactions occur under severe conditions (aggressive pH, high pressure, elevated temperature) and entail chemical degradation reactions (depolymerization) along with the synthesis of functionalized cellulose.…”

Section: Selective Oxidation Of Cellulose By Different Methodsmentioning

confidence: 99%

Selective Oxidation of Cellulose—A Multitask Platform with Significant Environmental Impact

Duceac¹,

Tanasă²,

Coseri³

2022

Materials

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Raw cellulose, or even agro-industrial waste, have been extensively used for environmental applications, namely industrial water decontamination, due to their effectiveness, availability, and low production cost. This was a response to the increasing societal demand for fresh water, which made the purification of wastewater one of the major research issue for both academic and industrial R&D communities. Cellulose has undergone various derivatization reactions in order to change the cellulose surface charge density, a prerequisite condition to delaminate fibers down to nanometric fibrils through a low-energy process, and to obtain products with various structures and properties able to undergo further processing. Selective oxidation of cellulose, one of the most important methods of chemical modification, turned out to be a multitask platform to obtain new high-performance, versatile, cellulose-based materials, with many other applications aside from the environmental ones: in biomedical engineering and healthcare, energy storage, barrier and sensing applications, food packaging, etc. Various methods of selective oxidation have been studied, but among these, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl) (TEMPO)-mediated and periodate oxidation reactions have attracted more interest due to their enhanced regioselectivity, high yield and degree of substitution, mild conditions, and the possibility to further process the selectively oxidized cellulose into new materials with more complex formulations. This study systematically presents the main methods commonly used for the selective oxidation of cellulose and provides a survey of the most recent reports on the environmental applications of oxidized cellulose, such as the removal of heavy metals, dyes, and other organic pollutants from the wastewater.

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“…In general, different experimental conditions (Table 1) are reported for the oxidation of aldohexoses, in terms of nitric acid concentration, reaction temperature, co-oxidant (i. e. nitrites), and atmosphere (air, O 2 , N 2 ). [46,47,48,49] A great variability in nitric acid oxidation protocols is also found for other substrates. [48,51] Therefore, the oxidation of galactose (Gal) to the corresponding meso-galactaric acid using nitric acid as the oxidant was studied thoroughly, in order to give better insights on the acid concentration needed, reaction temperature, and product recovery.…”

Section: Experimental Investigationmentioning

confidence: 99%

“…The experimental observation of the red-orange gases (i. e. NO 2 ) can be explained by the known reaction (Eq. 3): [49]…”

Section: Computational Investigationmentioning

confidence: 99%

The oxidation of d‐galactose into mucic acid (galactaric acid): experimental and computational insights towards a bio‐based platform chemical

Pasquale,

Chiacchio,

Acciaretti

et al. 2024

Asian J Org Chem

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Aldaric acids are becoming valuable platform chemicals in bioeconomy and circular economy approaches. Among them, mucic acid (meso‐galactaric acid) is gaining industrial attention as a bio‐based precursor of adipic acid found in polyamides, and of 2,5‐furan dicarboxylic acid, a valuable substitute for terephthalic acid in polyesters. A combination of detailed experimental protocols and conditions with DFT computational calculations for the synthesis of mucic acid from galactose are herein described. The product is obtained by reaction with diluted aqueous nitric acid as the oxidizing agent and the reaction medium. Optimized reaction conditions require 5 M nitric acid, 95 °C, galactose/HNO3 molar ratio 1:9, 100 g/L galactose concentration in the reaction medium. Computational calculations suggest that the oxidation mechanism may involve a contextual oxygen protonation and nitrate nucleophilic attack, leading to the oxidized product. The proposed mechanism requires a stoichiometry of 6 moles of nitric acid per galactose mole, albeit both experimental and computational data evidence that proton excess may be necessary to start the reaction. The reported study gives useful insights for the production of galactaric acid.

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Oxidation of D-Galactose and Cellulose with Nitric Acid, Nitrous Acid and Nitrogen Oxides

Cited by 28 publications

References 0 publications

Furan-2,5- and Furan-2,3-dicarboxylate Esters Derived from Marine Biomass as Plasticizers for Poly(vinyl chloride)

Furan-2,5- and Furan-2,3-dicarboxylate Esters Derived from Marine Biomass as Plasticizers for Poly(vinyl chloride)

Selective Oxidation of Cellulose—A Multitask Platform with Significant Environmental Impact

The oxidation of d‐galactose into mucic acid (galactaric acid): experimental and computational insights towards a bio‐based platform chemical

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