Synthesis of γ-Pyrones and <i>N</i>-Methyl-4-pyridones via the Au Nanoparticle-Catalyzed Cyclization of Skipped Diynones in the Presence of Water or Aqueous Methylamine

Zantioti-Chatzouda, Elisavet-Maria; Kotzabasaki, Vasiliki; Stratakis, Manolis

doi:10.1021/acs.joc.2c00627

Cited by 13 publications

(11 citation statements)

References 58 publications

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“…Increasing the AW/MD from 0 to 1.5 raised polysaccharide content of feedstock mixture linearly and decreased the pH of feedstock mixture exponentially, that is, from pH 7.1 to 5.5 (see Figure ). The decreasing feedstock pH to 5.5 enhanced the conversion of polysaccharides into biocrude oil due to higher selectivity for the formation of pyrones, cyclic C 5 -ketones, and furandiones (see Table S19) via dehydration of polysaccharides’ monomers into 5-HMF and furfural followed by isomerization, , Piancatelli rearrangement, and cyclization, respectively. In addition, a feedstock pH of around 5.5 has been reported to induce 5-HMF rehydration and lignin acidolysis with formic acid and formaldehyde as the side products, respectively.…”

Section: Resultsmentioning

confidence: 99%

Sustainable Resource Recovery from Dairy Waste: A Case Study of Hydrothermal Co-liquefaction of Acid Whey and Anaerobic Digestate Mixture

Sudibyo

Tester

2023

Energy Fuels

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Uncontrolled emission of carbon and nutrients due to mismanagement of dairy waste leads to global warming, eutrophication of water bodies, aerosol pollution, and acidification of ecosystems. We studied hydrothermal liquefaction (HTL) to sustainably recover resources by converting the dairy wastes into carbon-dense biocrude oil and a nutrient-rich aqueous-phase coproduct. We evaluated acid whey as an alternative source of acid catalyst, replacing acetic acid, for the HTL of anaerobically digested cattle manure (manure digestate). Using well-designed HTL experiments, we investigated the effects of several factors on the product formation and the fate of elements as well as the underlying chemistry. The investigated factors included reaction temperature (280−360 °C), reaction time (10−50 min), mixing ratio of acid whey to manure digestate (AW/MD of 0−2), and the amount of additional acetic acid required, that is, specified based on the final feedstock pH between 3.5 and 5.5. The experimental results suggested the following optimal conditions for enhanced biocrude oil formation and maximal nutrient yield in the aqueous-phase coproduct: AW/MD of 1.21, feedstock mixture pH of 4.5, and reaction temperature and time of 354 °C and 21 min, respectively. Under such conditions, the biocrude oil yield was enhanced to 40−50% (equivalent to 60−80% energy recovery) via cyclic acetalization, hydroxymethylation, isomerization, Piancatelli rearrangement, oxidation, and condensation with heteroatom removal via several deoxygenation and denitrogenation mechanisms. Moreover, these conditions provided adequate acidification to solubilize Mg-carbonate and Ca-phosphate minerals and catalyzed the deamination of N-heterocyclics and other nitrogenous compounds, producing a higher recoverable yield of Mg, NH 3 -N, P, and K nutrients in the aqueous-phase coproduct, that is, 60−70, 30−40, ∼40, and >95%, respectively. This study demonstrated the potential of using HTL for coprocessing manure digestate and acid whey to measurably valorize biomass waste as a key component of achieving a circular bioeconomy for the dairy industry.

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Section: Resultsmentioning

confidence: 99%

Sustainable Resource Recovery from Dairy Waste: A Case Study of Hydrothermal Co-liquefaction of Acid Whey and Anaerobic Digestate Mixture

Sudibyo

Tester

2023

Energy Fuels

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“…A possible explanation for this discrepancy is that 1a rearranges or degrades on the gold surface. Indeed, while our work was in progress, it was reported that related diynones rearrange to γ-pyrones in the presence of gold nanoparticles supported on titania (Au/TiO 2 ) in solution, initiated by the aurophilicity of the triple bonds . We, therefore, synthesized the corresponding γ-pyrone derivative 4 by acid-catalyzed rearrangement of 1a following a literature route: compound 4 would be the expected product of the Au-catalyzed rearrangement of 1a .…”

Section: Resultsmentioning

confidence: 99%

Electronic Conductance and Thermopower of Cross-Conjugated and Skipped-Conjugated Molecules in Single-Molecule Junctions

et al. 2023

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We report a combined experimental and theoretical study of a series of thiomethyl (SMe) anchored cross-conjugated molecules featuring an acyclic central bridging ketone and their analogous skipped-conjugated alcohol derivatives. Studies of these molecules in a gold|single-molecule|gold junction using scanning tunneling microscopy-break junction techniques reveal a similar conductance (G) value for both the cross-conjugated molecules and their skipped-conjugated partners. Theoretical studies based on density functional theory of the molecules in their optimum geometries in the junction reveal the reason for this similarity in conductance, as the predicted conductance for the alcohol series of compounds varies more with the tilt angle. Thermopower measurements reveal a higher Seebeck coefficient (S) for the cross-conjugated ketone molecules relative to the alcohol derivatives, with a particularly high S for the biphenyl derivative 3a (−15.6 μV/K), an increase of threefold compared to its alcohol analog. The predicted behavior of the quantum interference (QI) in this series of cross-conjugated molecules is found to be constructive, though the appearance of a destructive QI feature for 3a is due to the degeneracy of the HOMO orbital and may explain the enhancement of the value of S for this molecule.

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“…The chemistry of these heterocycles is actively developed not only for the design of biologically important compounds [ 7 , 8 , 9 ], but also for effective preparation in the industry [ 1 , 2 , 3 , 10 , 11 , 12 , 13 , 14 , 15 ]. At the same time, there is a need to search for new multifarious pyridone building blocks [ 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 ] and convenient synthetic tools for the construction of polycyclic pyridones [ 1 , 2 , 3 , 15 ], including CH functionalization [ 26 ].…”

Section: Introductionmentioning

confidence: 99%

The Construction of Polycyclic Pyridones via Ring-Opening Transformations of 3-hydroxy-3,4-dihydropyrido[2,1-c][1,4]oxazine-1,8-diones

et al. 2023

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This work describes the synthesis of 3-hydroxy-3,4-dihydropyrido[2,1-c][1,4]oxazine-1,8-diones, their tautomerism, and reactivity towards binucleophiles. These molecules are novel and convenient building-blocks for the direct construction of biologically important polycyclic pyridones via an oxazinone ring-opening transformation promoted with ammonium acetate or acetic acid. In the case of o-phenylenediamine, partial aromatization of the obtained heterocycles proceeded to form polycyclic benzimidazole-fused pyridones (33–91%).

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Synthesis of γ-Pyrones and N-Methyl-4-pyridones via the Au Nanoparticle-Catalyzed Cyclization of Skipped Diynones in the Presence of Water or Aqueous Methylamine

Cited by 13 publications

References 58 publications

Sustainable Resource Recovery from Dairy Waste: A Case Study of Hydrothermal Co-liquefaction of Acid Whey and Anaerobic Digestate Mixture

Sustainable Resource Recovery from Dairy Waste: A Case Study of Hydrothermal Co-liquefaction of Acid Whey and Anaerobic Digestate Mixture

Electronic Conductance and Thermopower of Cross-Conjugated and Skipped-Conjugated Molecules in Single-Molecule Junctions

The Construction of Polycyclic Pyridones via Ring-Opening Transformations of 3-hydroxy-3,4-dihydropyrido[2,1-c][1,4]oxazine-1,8-diones

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