Succinimide-Based Ionic Liquids: An Efficient and Versatile Platform for Transformation of CO2 into Quinazoline-2,4(1H,3H)-diones under Mild and Solvent-Free Conditions

Liu, Fusheng; Ping, Ran; Zhao, Penghui; Gu, Yongqiang; Gao, Jun; Liu, Mengshuai

doi:10.1021/acssuschemeng.9b03154

Cited by 33 publications

(11 citation statements)

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“…By 1 H NMR analysis, two obvious changes for the proton signal of amino in 2-aminobenzonitrile appeared after interacting with [HTMG][Triz] (Figure 4). On the one hand, the proton signal (H-e) became broader and had a clear downfield shift from δ = 6.000 to 6.035 ppm; it might be because of the activation of the amino group by forming hydrogen bonds with the [HTMG] + cation, and the result was consistent with some other reported catalysts; 11,20,40 on the other hand, there appeared a new proton signal at δ = 6.903 ppm, which possibly be resulted from the strong interaction between the proton (H-f) with the [Triz] − anion. 20 Clearly, the changes indicated that both the cation and anion of the [HTMG][Triz] could weaken the N−H bond in the NH 2 group to activate the 2-aminobenzonitrile effectively.…”

Section: ■ Results and Discussionsupporting

confidence: 87%

Efficient One Pot Capture and Conversion of CO₂ into Quinazoline-2,4(1H,3H)-diones Using Triazolium-Based Ionic Liquids

Liu

Ping

et al. 2020

ACS Sustainable Chem. Eng.

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CO2 capture and utilization (CCU) have aroused much attention. In this paper, several novel triazolium-based ionic liquids (ILs) were developed for highly efficient transformation of CO2 into quinazoline-2,4(1H,3H)-diones. The catalytic behaviors such as the effects of IL structures and reaction parameters, catalyst recyclability, and scope of substrates were studied in detail. As compared to the reported homogeneous and heterogeneous catalysts, the [HTMG][Triz] with a tetramethylguanidine cation and a triazole anion exhibited an exceptional activity at 50 °C and 1 atm CO2 without any organic solvents. On the basis of the CCU strategy, we first studied the equimolar CO2 capture by the [HTMG][Triz] and one pot conversion of activated CO2 into various quinazoline-2,4(1H,3H)-diones, and good to excellent product yields were obtained. In addition, the catalytic performance for synthesis of quinazoline-2,4(1H,3H)-dione under low concentration of CO2 using a simulated flue gas was studied. The developed triazolium-based ILs could realize simultaneous activation of CO2 and the substrates under ambient conditions, which also have been demonstrated to support the reaction mechanism well. The integrative protocol here shows great significance in the practical synthesis of quinazoline-2,4(1H,3H)-dione and their derivatives from captured CO2 waste under mild conditions.

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Section: ■ Results and Discussionsupporting

confidence: 87%

Efficient One Pot Capture and Conversion of CO₂ into Quinazoline-2,4(1H,3H)-diones Using Triazolium-Based Ionic Liquids

Liu

Ping

et al. 2020

ACS Sustainable Chem. Eng.

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“…The cyclization of 2-aminobenzonitriles with CO 2 is an atom-economical route to accessing quinazoline-2,4(1 H ,3 H )-diones, which generally requires metal catalysts and high temperature and pressure. Basic ILs with anions such as acetate, azolate, , phenolate, and the succinimide anion were found to be capable of catalyzing this reaction due to the cooperative effects of cations and anions (Scheme A). We designed protic ILs based on the neutralization reaction of superbases (e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene, DBU) with trifluoroethanol (TFE), which could capture CO 2 with equimolar uptake via forming anionic carbonate, [TFECOO] − , under ambient conditions .…”

Section: Ionic-liquid-catalyzed Strategies For the Transformation Of ...mentioning

confidence: 99%

Ionic-Liquid-Catalyzed Approaches under Metal-Free Conditions

2021

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Conspectus Metal-free catalysis is a promising protocol to access chemicals without metal contamination. Ionic liquids (ILs) that are entirely composed of organic cations and inorganic/organic anions have emerged as promising alternatives to molecular solvents and metal catalysts due to their unique properties such as structural tunability, the coexistence of multiple interactions among ions (e.g., electrostatic interaction, hydrogen bonding, van de Waals forces, acid/base interactions, hydrophilic/hydrophobic interactions, etc.), unique affinity for a wide range of chemicals, good chemical and thermal stability, and quite low volatility. ILs have shown potential applications in various chemical processes. In this Account, we systematically described our most recent work on IL-catalyzed approaches under metal-free conditions. The first section presents the IL-catalyzed strategies toward the transformation of CO2 to value-added chemicals, focusing on the CO2-reactive IL-catalyzed CO2 transformation to various heterocycles and the IL-catalyzed reductive transformation of CO2 to chemicals. In these approaches, we designed task-specific ILs that are able to chemically capture and activate CO2 via forming anion-based carbonate/carbamate or cation-based carboxylate/carbamate intermediates, thus further accomplishing its transformation to a series of heterocycles including quinazoline-2,4(1H,3H)-diones, cyclic carbonates, 2-oxazolidinones, oxazolones, and benzimidazolones under metal-free conditions. For the IL-catalyzed approaches to reducing CO2 with hydrosilanes to chemicals, we employed ILs capable of activating the Si–H bond in hydrosilanes and the N–H bond in amine substrates via H-bonding, thus achieving the reductive transformation of CO2 to formamides, benzimidazoles, and benzothiazoles via cooperative catalysis. The second section describes our finding on the IL-catalyzed hydration of the CC bond in propargylic alcohols. Azolate anion-based ILs that can chemically capture CO2 via the formation of carbamates could serve as robust nucleophiles to attack the CC bond in propargylic alcohols and then efficiently catalyze the hydration of propargylic alcohols to produce α-hydroxy ketones with the assistance of atmospheric CO2 gas under metal-free conditions. The third section unveils the cooperative catalysis strategy of hydrogen bond donors and acceptors of ILs for chemical reactions. In the hydrogen-bonding catalysis protocols, cations of the ILs act as H-bond donors and anions, as acceptors, forming H-bonds with the reactant molecules, respectively, in opposite ways, which can cooperatively catalyze the ring-closing C–O/C–O bond metathesis reactions of aliphatic diethers to O-heterocycles, the dehydrative etherification of alcohols to ethers, and direct oxidative esterification of alcohols to esters. We believe that these IL-catalyzed metal-free processes and strategies display promising practical applications, and their commercialization would bring great benefits to the production of the as-afforded value-...

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“…These puzzling phenomena encourage us to perform a detailed density functional theory (DFT) study, from which we expect to reveal (i) whether the mechanism proposed by Liu et al is applicable for understanding the high catalytic activity of [HDBU + ][TFE – ] with regards to the synthesis of quinazoline-2,4-(1 H ,3 H )-diones from 2-aminobenzonitriles reacting with CO 2 , (ii) if not, what the alternative molecular mechanism should be, (iii) what the nature of these puzzling phenomena shown in Table is. Our DFT calculations are expected to present a clear picture of how the protic ILs catalyze the titled reaction and to provide useful guidance for preparing quinazoline-2,4-(1 H ,3 H )-diones from the reactions of 2-aminobenzonitriles with CO 2 reasonably. ,− …”

Section: Introductionmentioning

confidence: 99%

How and Why a Protic Ionic Liquid Efficiently Catalyzes Chemical Fixation of CO₂ to Quinazoline-2,4-(1H,3H)-diones: Electrostatically Controlled Reactivity

Han

Liu

2019

J. Phys. Chem. A

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A density functional theory study has been conducted to gain insight into the intriguing experimental observations on the synthesis of quinazoline-2,4-(1H,3H)-diones from 2-aminobenzonitriles reacting with CO 2 catalyzed by protic ionic liquids (ILs). We explored the molecular mechanism of the titled reaction, as well as the origin and catalytic nature of different ILs toward the reaction in detail. The calculated energetically viable mechanism involves CO 2 attack, intramolecular rearrangement, and intramolecular cyclization stages. This mechanism features the initial polarization of the CN triple bond with the assistance of the real catalytic species, [HDBU + ][TFECOO − ], where the cation [HDBU + ] acts as Brønsted acid and the anion [TFECOO − ], the adduct of anion [TFE − ] and CO 2 , acts as a nucleophile. The calculated results present the electrostatically controlled character of the reaction, where the reactivity relies on the electrostatic interaction of the IL cation with the anion. The reactivity can be controlled and regulated by the basicity of the deprotonated counterpart of the IL cation as well as the CO 2 adsorption ability of the IL anion. The best catalytic performance of [HDBU + ][TFE − ] is attributed to its strongest basicity of the deprotonated counterpart of [HDBU + ] and its most efficient CO 2 adsorption property of [TFE − ]. These theoretical results are expected to provide guidance for designing efficient IL-based catalysts in preparing quinazoline-2,4-(1H,3H)-diones by reacting 2aminobenzonitriles with CO 2 .

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Succinimide-Based Ionic Liquids: An Efficient and Versatile Platform for Transformation of CO₂ into Quinazoline-2,4(1H,3H)-diones under Mild and Solvent-Free Conditions

Cited by 33 publications

References 35 publications

Efficient One Pot Capture and Conversion of CO₂ into Quinazoline-2,4(1H,3H)-diones Using Triazolium-Based Ionic Liquids

Efficient One Pot Capture and Conversion of CO₂ into Quinazoline-2,4(1H,3H)-diones Using Triazolium-Based Ionic Liquids

Ionic-Liquid-Catalyzed Approaches under Metal-Free Conditions

How and Why a Protic Ionic Liquid Efficiently Catalyzes Chemical Fixation of CO₂ to Quinazoline-2,4-(1H,3H)-diones: Electrostatically Controlled Reactivity

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Succinimide-Based Ionic Liquids: An Efficient and Versatile Platform for Transformation of CO2 into Quinazoline-2,4(1H,3H)-diones under Mild and Solvent-Free Conditions

Cited by 33 publications

References 35 publications

Efficient One Pot Capture and Conversion of CO2 into Quinazoline-2,4(1H,3H)-diones Using Triazolium-Based Ionic Liquids

Efficient One Pot Capture and Conversion of CO2 into Quinazoline-2,4(1H,3H)-diones Using Triazolium-Based Ionic Liquids

Ionic-Liquid-Catalyzed Approaches under Metal-Free Conditions

How and Why a Protic Ionic Liquid Efficiently Catalyzes Chemical Fixation of CO2 to Quinazoline-2,4-(1H,3H)-diones: Electrostatically Controlled Reactivity

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Product

Resources

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Succinimide-Based Ionic Liquids: An Efficient and Versatile Platform for Transformation of CO₂ into Quinazoline-2,4(1H,3H)-diones under Mild and Solvent-Free Conditions

Efficient One Pot Capture and Conversion of CO₂ into Quinazoline-2,4(1H,3H)-diones Using Triazolium-Based Ionic Liquids

Efficient One Pot Capture and Conversion of CO₂ into Quinazoline-2,4(1H,3H)-diones Using Triazolium-Based Ionic Liquids

How and Why a Protic Ionic Liquid Efficiently Catalyzes Chemical Fixation of CO₂ to Quinazoline-2,4-(1H,3H)-diones: Electrostatically Controlled Reactivity