Reactivity of [60]Fullerene with Primary Nitro Compounds: Addition or Catalysed Condensation to Isoxazolo[60]fullerenes

Biagiotti, Giacomo; Cicchi, Stefano; Sarlo, Francesco De; Machetti, Fabrizio

doi:10.1002/ejoc.201402990

Cited by 12 publications

(6 citation statements)

References 78 publications

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“…Nitroacetamide ( 1 ) and N , N -dimethylnitroacetamide ( 3 ) have been obtained, respectively, by aminolysis from ethyl nitroacetate [32,33] and methyl nitroacetate [34], following previously reported procedures.…”

Section: Methodsmentioning

confidence: 99%

Understanding the Exceptional Properties of Nitroacetamides in Water: A Computational Model Including the Solvent

Penna

Machetti

2018

Molecules

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Proton transfer in water involving C–H bonds is a challenge and nitro compounds have been studied for many years as good examples. The effect of substituents on acidity of protons geminal to the nitro group is exploited here with new pKa measurements and electronic structure models, the latter including explicit water environment. Substituents with the amide moiety display an exceptional combination of acidity and solubility in water. In order to find a rationale for the unexpected pKa changes in the (ZZ′)NCO- substituents, we measured and modeled the pKa with Z=Z′=H and Z=Z′=methyl. The dominant contribution to the observed pKa can be understood with advanced computational experiments, where the geminal proton is smoothly moved to the solvent bath. These models, mostly based on density-functional theory (DFT), include the explicit solvent (water) and statistical thermal fluctuations. As a first approximation, the change of pKa can be correlated with the average energy difference between the two tautomeric forms (aci and nitro, respectively). The contribution of the solvent molecules interacting with the solute to the proton transfer mechanism is made evident.

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Section: Methodsmentioning

confidence: 99%

Understanding the Exceptional Properties of Nitroacetamides in Water: A Computational Model Including the Solvent

Penna

Machetti

2018

Molecules

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“…Materials: Commercially available (Lancaster and Aldrich) ethyl nitroacetate ( 1a ), methyl nitroacetate ( 1b ), benzoylnitromethane ( 1e ), nitroethane ( 1g ), nitropentane ( 1h ), and organic bases, 99 %, were used as supplied. Diethyl (nitromethyl)phosphonate ( 1f ) was prepared following a previously reported procedure . N ‐Methyl‐2‐nitroacetamide ( 1c ) was prepared following a previously reported procedure .…”

Section: Methodsmentioning

confidence: 99%

Competitive Copper Catalysis in the Condensation of Primary Nitro Compounds with Terminal Alkynes: Synthesis of Isoxazoles

et al. 2016

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Isoxazoles, mainly 3,5‐disubstituted, are prepared by catalytic condensation of primary nitro compounds with terminal acetylenes by using a copper/base catalytic system. The additional catalytic effect of the copper(II) salts is evidenced by comparing the kinetic profiles. Selectivity dependence on reaction conditions is considered for phenylacetylene in the following competitive processes: oxidative coupling of terminal alkynes to conjugated diynes catalyzed by CuII and base in the presence of air; production of furazans beside condensation with benzoylnitromethane to 3‐benzoylisoxazoles, as a result of the reaction of the dipolarophile with 3,4‐dibenzoylfuroxan; addition of electron‐poor alkynes (e.g., methyl propiolate) with themselves and with the nitro compound. Thus, oxidative coupling is negligible in reactions with “active” nitro compounds, whereas with nitroalkanes both products are observed: only trace amounts of isoxazoles are detected without copper. Similarly, in the presence of copper, 3‐benzoyl‐5‐phenylisoxazole is predominant over the furazan. Furthermore, condensations of electron‐poor alkynes give complex reaction mixtures in the presence of base alone, but cycloadducts are conveniently prepared with copper. The results indicate the practical and general utility of this catalytic method for synthetic practice.

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“…Among different fullerenes illustrated in Figure 3, C 60 has gained much attention due to its chemical reactivity [48], hydrogen storage capability [49], and for the six one-by-one-electron reduction behavior [50]. These attractive properties are counterbalanced by a very high cost that inhibits C 60 use at a large scale.…”

Section: Fullerene-based Actuatorsmentioning

confidence: 99%

Carbon Nanostructures for Actuators: An Overview of Recent Developments

Giorcelli

Bartoli

2019

Actuators

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In recent decades, micro and nanoscale technologies have become cutting-edge frontiers in material science and device developments. This worldwide trend has induced further improvements in actuator production with enhanced performance. A main role has been played by nanostructured carbon-based materials, i.e., carbon nanotubes and graphene, due to their intrinsic properties and easy functionalization. Moreover, the nanoscale decoration of these materials has led to the design of doped and decorated carbon-based devices effectively used as actuators incorporating metals and metal-based structures. This review provides an overview and discussion of the overall process for producing AC actuators using nanostructured, doped, and decorated carbon materials. It highlights the differences and common aspects that make carbon materials one of the most promising resources in the field of actuators.

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Reactivity of [60]Fullerene with Primary Nitro Compounds: Addition or Catalysed Condensation to Isoxazolo[60]fullerenes

Cited by 12 publications

References 78 publications

Understanding the Exceptional Properties of Nitroacetamides in Water: A Computational Model Including the Solvent

Understanding the Exceptional Properties of Nitroacetamides in Water: A Computational Model Including the Solvent

Competitive Copper Catalysis in the Condensation of Primary Nitro Compounds with Terminal Alkynes: Synthesis of Isoxazoles

Carbon Nanostructures for Actuators: An Overview of Recent Developments

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