Equilibrium Acidities of Nitroalkanes in an Ionic Liquid

Gao, Fulin; Ji, Pengju; Cheng, Jiang

doi:10.1021/acs.joc.8b02183

Cited by 8 publications

(8 citation statements)

References 68 publications

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“…The method for the acidity measurement is introduced in details in the Supporting Information and our previous work . In specific, the indicator p K a scales for PILs [BpyH][NTf 2 ] and [PyH 2 ][NTf 2 ] were constructed stepwise.…”

Section: Results and Discussionmentioning

confidence: 99%

“…The AIL [Bmpy][NTf 2 ] was synthesized according to the previously reported procedures, and the water content was less than 10 ppm, which was determined by the general Karl Fisher titration method. The PIL [BpyH][NTf 2 ] and [PyH 2 ][NTf 2 ] were prepared by an ion exchange method (vide infra), and the water content was less than 50 ppm.…”

Section: Methodsmentioning

confidence: 99%

“…The especially made UV cells for the p K a determinations were similar to the previously described method . The acidities of various substrate acids were determined by employing appropriate acid indicator(s) described in Figures S3 and S4.…”

Section: Methodsmentioning

confidence: 99%

“…The bases used for deprotonation of indicators were 1-butylpyrrolidine and pyrrolidine in [BpyH][NTf 2 ] and [PyH 2 ][NTf 2 ], respectively, and that in [Bmpy][NTf 2 ] was the same as that reported previously . The principle of p K a measurement by the UV–Vis method is the same as before and briefly introduced as follows: where, in eqs eqs and eqs , HIn and HA denote the indicator and substrate acids, respectively. In a typical measurement process, first, an indicator acid (HIn) with the known p K a value was completely deprotonated by the base.…”

Section: Methodsmentioning

confidence: 99%

“…It is well known that systematic studies of acid–base equilibria in solutions may provide useful insights into the solute–solvent interactions at both macro and micro level . It has been shown by us that systematically and precisely determined p K a s in neat AILs can be a powerful approach to reveal several subtle but fundamentally distinctive features of AILs. , However, surprisingly, till now similar studies in this respect in PILs are rare, and the effects of the cation and anion on the solvation chemistry in PILs remain practically elusive.…”

Section: Introductionmentioning

confidence: 99%

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Unexpected Strong Acidity Enhancing the Effect in Protic Ionic Liquids Quantified by Equilibrium Acidity Studies: A Crucial Role of Cation Structures on Dictating the Solvation Properties

Gao

Cheng

2020

J. Org. Chem.

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The equilibrium acidities for several series of structural and electronic different organic acids were measured in 3-pyrrolidinium-based aprotic and protic ionic liquid (IL) analogues, that is, [Bmpy][NTf2], [BpyH][NTf2], and [PyH2][NTf2], by the UV–Vis method. The acidities of neutral acids are found to be much stronger in the protic ILs (PILs) than aprotic ILs (AILs), and the acidifying effect in the two PILs roughly increases proportionally to the number of protons in the cation of the PIL. On the other hand, interestingly, the cationic N+–H acids exhibit similar acidities in [Bmpy][NTf2] and [BpyH][NTf2] but much weaker than those in [PyH2][NTf2]. The Hammett ρ values for the acidic dissociation of para-substituted benzoic acids in two PILs are about the same as that in water (1.00) but significantly smaller than that in the AIL [Bmpy][NTf2] (2.66). The correlations between the acidities in the PILs and water show double-linear relationships with different slopes and intercepts for the neutral and cationic acids. These, together with previous observations in the PILs [DBUH][OTf] (DBU = 1,5-diazabicyclo(5.4.0)-5-undecene) and EAN (ethylammonium nitrate), clearly indicate that the structure of the cation plays a subtle but a crucial role on sensing the electronic nature of solutes and strongly affects the solvation behaviors of PILs.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Unexpected Strong Acidity Enhancing the Effect in Protic Ionic Liquids Quantified by Equilibrium Acidity Studies: A Crucial Role of Cation Structures on Dictating the Solvation Properties

Gao

Cheng

2020

J. Org. Chem.

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Traps for Electrons and Holes Limit the Efficiency and Durability of Polymer Light‐Emitting Electrochemical Cells

Diethelm

Devižis

et al. 2022

Adv Funct Materials

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Polymer light-emitting electrochemical cells (PLECs) and light-emitting diodes (PLEDs) receive interest for large-area lighting and signage applications. During operation of a PLEC, a p-i-n junction develops where electrons and holes are injected into the film and are transported along n-and p-doped regions to the intrinsic (i) region, where they recombine under light emission. Conceptually, this resembles the PLED device architecture equipped with Ohmic charge-injection and transport layers. The similarity between the i-region of the PLEC and the emissive layer of the PLED is obvious; however, implication of this has not been examined in detail so far. For example, for PLEDs it is known that electron traps hinder the electron transport, and that hole trap formation dictates the long-term durability. Here, for PLECs the electrical and optical response to electrical driving and breaks are studied, the current response to external light irradiation is probed, and degradation is followed with long-term absorption and capacitance measurements. The electron traps in PLECs are identified and it is found that hole trap formation limits the device lifetime, in the same manner as established for PLEDs. It is concluded that charge traps in semiconducting polymers present important, but so far overlooked intrinsic performance limitations for PLECs.

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Copper‐Catalyzed α‐Arylation of Nitroalkanes with (Hetero)aryl Bromides/Iodides

Huang,

Li,

et al. 2024

Angewandte Chemie

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α‐Aryl substituted nitroalkanes are valuable synthetic building blocks that can be easily converted into a‐aryl substituted aldehydes, ketones, carboxylic acids, as well as amines. Herein, an efficient Cu/oxalamide‐catalyzed coupling between nitroalkanes and (hetero)aryl halides (Br, I) was developed to direct access highly diverse α‐aryl substituted nitroalkanes. Compared with the current state of art, this protocol is more environmentally friendly and practical for synthetic chemists. This approach is characterized by a broad substrate scope on both nitroalkane part (primary nitroalkanes and nitromethane) and sp2 halide part ((hetero)aryl bromides/iodides and alkenyl bromides/iodides). The excellent functional group tolerance was observed, which would enable real world synthetic applications. More importantly, TON of current transformation reached to 3640, when some aryl iodides were used as coupling partners. This represents currently the highest catalyst turnover for transition‐metal catalyzed α‐arylation of nitroalkanes. Furthermore, the successful application in late‐stage modification of complex molecules and synthesis of a known retinoid X receptor (RXR) antagonist exemplified its synthetic potential.

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Equilibrium Acidities of Nitroalkanes in an Ionic Liquid

Cited by 8 publications

References 68 publications

Unexpected Strong Acidity Enhancing the Effect in Protic Ionic Liquids Quantified by Equilibrium Acidity Studies: A Crucial Role of Cation Structures on Dictating the Solvation Properties

Unexpected Strong Acidity Enhancing the Effect in Protic Ionic Liquids Quantified by Equilibrium Acidity Studies: A Crucial Role of Cation Structures on Dictating the Solvation Properties

Traps for Electrons and Holes Limit the Efficiency and Durability of Polymer Light‐Emitting Electrochemical Cells

Copper‐Catalyzed α‐Arylation of Nitroalkanes with (Hetero)aryl Bromides/Iodides

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