- Reversible phase transformation gel-type ionic liquid compounds based on tungstovanadosilicates
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A series of new reversible phase transformation gel-type ionic liquid compounds, [PyPS]5SiW11VO40, [PyPS]7SiW9V3O40, [TEAPS]5SiW11VO40 and [TEAPS]7SiW9V3O40, have been synthesized from two organic ammoniums 1-(3-sulfonic group) propyl-pyridine (PyPS), 1-(3-sulfonic group) propyl-triethylammonium (TEAPS) and vanadium-substituted heteropoly acids H5SiW11VO40 and H7SiW9V3O40. The products can undergo a phase transformation from viscous gel-state to liquid-state below 100 °C, and ionic conductivity up to 10-3 S cm-1 was observed at 110 °C for these gel-type POM-ILs. The relationship between the component elements of the products and their physicochemical property has been studied. Their thermostability was measured using thermogravimetric and differential thermal analysis (TG-DTA), and the result indicates that the less vanadium atoms there are inside the heteropoly anion, the more stable the POM-IL is at high temperature. Cyclic voltammetry is carried out to study their electrochemical properties in organic solution. The potential values of redox waves confirm that the oxidability of these gel-type POM-ILs can be controlled upon changing the number of vanadium atoms in the heteropolyanions.
- Huang, Tianpei,Xie, Zhirong,Wu, Qingyin,Yan, Wenfu
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- Heteropolyacid-based ionic liquids as effective catalysts for the synthesis of benzaldehyde glycol acetal
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A series of environmental benign ionic liquid (IL) catalysts, synthesized by incorporating varied amounts of tungstophosphoric acid (TPA) and pyridinium propyl sulfobetaine (PPS) zwitterionic precursor, were exploited for homogeneous conversion of biomass. In particular, these water-soluble PPS-TPA IL ([PPSH]xH3-xPW12O40; x = 1.0-3.0) catalysts were evaluated for acetalization of benzaldehyde with glycol. The catalyst system revealed self-separation characteristics, which resulted in the formation of biphasic product/catalyst layers to render facile product separation and catalyst recycling. Among various PPS-TPA ILs examined, the [PPSH]2HPW12O40 catalyst exhibited excellent durability and an optimal acetal yield over 85%, in good agreement with that predicted by factorial design of experiments and response surface methodology (RSM). The effects and correlations of different experimental variables such as reaction time, relative reactant concentration, amount of water-carrying agent, and amount of catalyst were addressed by the Box-Behnken design (BBD). The deduced optimal conditions lead to an acetal yield of 85.2%, which is consistent with experimental results and that predicted by the BBD model. The superior acetalization activities observed for the novel PPS-TPA IL catalysts are attributed to their highly acidic nature and weak mass transport resistance.
- Han, Xiaoxiang,Yan, Wei,Chen, Keke,Hung, Chin-Te,Liu, Li-Li,Wu, Pei-Hao,Huang, Shing-Jong,Liu, Shang-Bin
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- The synthesis and electrical properties of hybrid gel electrolytes derived from Keggin-type heteropoly acids and 3-(pyridin-1-ium-1-yl)propane-1-sulfonate (PyPs)
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Herein, we report the effect of the proton concentration in polyoxometalates (POMs) upon hybrid formation with ionic liquids (ILs), and their ionic conductivity relationship to optimize their ionic conductivity. The hybrid gels were derived from Keggin-type heteropoly acids containing different proton concentrations, such as H3PW11MoO40, H4PMo11VO40 and H5PMo10V2O40, and 3-(pyridin-1-ium-1-yl)propane-1-sulfonate (PyPs) IL. Elemental C, H, and N analysis was found to be consistent with the theoretical composition within 4% for C and N, whereas H content was found to be slightly higher than the anticipated value, which may be due to potential uptake of water during the sample preparation. 1H and 13C nuclear magnetic resonance and Fourier transform infrared spectroscopy (FTIR) confirmed the presence of functional groups of PyPs in the hybrids. In situ variable temperature powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), electrochemical AC impedance spectroscopy and cyclic voltammetry studies showed excellent thermal (up to ～300 °C) and electrochemical (3 V at room temperature) stability of [PyPs]3PW11MoO40. The structural characterizations confirmed the interaction between the organic cation and Keggin-type inorganic heteropoly anion in the hybrid material. The bulk ionic conductivity of 0.1, 0.01 and 0.0003 S cm-1 at ～90 °C was obtained for [PyPs]3PW11MoO40, [PyPs]4PMo11VO40 and [PyPs]5PMo10V2O40, respectively.
- Narayanan, Sumaletha,Tong, Xia,Thangadurai, Venkataraman
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p. 102549 - 102556
(2016)
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- Synthesis of 9,9-bis(4-hydroxyphenyl) fluorene catalyzed by bifunctional ionic liquids
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Through structural design, a series of bifunctional ionic liquids (BFILs) containing sulfonic acid (-SO3H) and sulfhydryl groups (-SH) were synthesized and characterized by NMR and MS. The acidity of these BFILs was measured by the Hammett acidity (H0) and the effective sulfhydryl molar content of BFILs was determined by Ellman's method. Moreover, BFIL's catalytic properties in the condensation reaction of 9-fluorenone and phenol were studied. BFIL catalyst 6c can achieve nearly 100% conversion of 9-fluorenone with a high selectivity of 9,9-bis(4-hydroxyphenyl) fluorene (95.2%).
- Bai, Wei,Gao, Zhanxian,Lu, Xinxin,Wei, Jialun,Yan, Lei,Yu, Limei
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p. 32559 - 32564
(2021/12/07)
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- Dual targeting of cholinesterase and amyloid beta with pyridinium/isoquinolium derivatives
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With the surge in the cases of Alzheimer's disease (AD) over the years, several targets have been explored to curb the disease. Cholinesterases, namely acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE), remain to be the available targets that are amendable to currently approved treatments. In this study, a series of novel compounds based on tramiprosate, a highly specific amyloid beta (Aβ) inhibitor, was designed to inhibit AChE, BuChE, and Aβ aggregation. In particular, the addition of a pyridinium/isoquinolinium ring to the tramiprosate moiety (to give compounds 3a–j) led to an increase in the binding affinity for the catalytic active site of cholinesterase, which was hampered by the presence of sulfonic acid. Exclusion of the sulfonic acid moiety led to a novel but effective class of cholinesterase inhibitors (9a–w). in vitro Aβ aggregation inhibition assay indicated that compounds 3a–j, 9e–f, 9i–l, 9q, 9r, 9u–w, and 12 could inhibit over 10% Aβ aggregation at 1 mM concentration. Cholinesterase inhibition assay suggested that compounds 9g, 9h, 9o, and 9q–t exhibit over 70% inhibition on both AChE and BuChE at a concentration of 100 μM. Amongst the designed molecules, compound 9r (ca 18% at 1 mM) showed comparable inhibitory effect on the inhibition of Aβ aggregation with tramiprosate (ca 20% at 1 mM), along with impressive cholinesterase inhibitory potential (AChE IC50 = 13 μM and BuChE IC50 = 12 μM), acceptable toxicity and ability to pass through blood brain barrier, which could be used to ameliorate the phenotypes of AD in preclinical models.
- Chakravarty, Harapriya,Ju, Yaojun,Chen, Wen-Hua,Tam, Kin Y.
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p. 242 - 255
(2019/12/27)
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- Microwave-promoted one-pot three-component synthesis of 2,3-dihydroquinazolin-4(1H)-ones catalyzed by heteropolyanion-based ionic liquids under solvent-free conditions
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A series of 2,3-dihydroquinazoline-4(1H)-one derivatives have been synthesized via one-pot three-component reaction using isatoic anhydrides, amines and aldehydes (or ketones) catalyzed by heteropolyanion-based ionic liquids under microwave-promoted conditions. The practical protocol was found to tolerate a wide range of substrates with different functional groups. Moderate to excellent yields, solvent-free media and operational simplicity are the main highlights. Furthermore, the catalyst can be recovered and reused without evident loss of reactivity. This method provides a green and much improved protocol over the existing methods.
- Yang, Yang,Fu, Renzhong,Liu, Yang,Cai, Jing,Zeng, Xiaojun
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- Condensation of 9-fluorenone and phenol using an ionic liquid and a mercapto compound synergistic catalyst
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A series of ionic liquids (ILs) were synthesized and their Hammett acidities (H0) were determined using 4-nitroaniline as the indicator. The relationship among IL's structure, the acid strength, and the catalytic performance in the condensation reaction of 9-fluorenone with phenol was discussed. The effective H0 range of ionic liquids that can catalyse the condensation reaction was obtained. Moreover, the catalysis of the mercapto compound co-catalyst was also systematically studied. According to the analysis of how the structure of the sulfydryl co-catalyst affects the percent conversion of 9-fluorenone and the selectivity of BHPF, a mechanism for the reaction in the IL-thiol cooperative catalytic system was proposed. The present work gave a clear clue to design novel IL catalysts for the synthesis of BHPF.
- Lei, Yan,Yu, Limei,Shen, Maochang,Luo, Shikang,Gao, Zhanxian
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supporting information
p. 15700 - 15705
(2019/10/19)
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- Method of fabricating fatty acids through transacylation
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Fatty acids are produced through transacylation. An organic nitrogen-containing compound is reacted with alkyl sultone to generate a white solid of a zwitterionic compound. After being purified and dried, the white solid is powdered to be reacted with a Bronsted strong acid for obtaining a clear viscous water-based acidic ionic liquid (IL) as a catalyst used used to effectively process transacylation between oil and acetic acid (HOAc) for fabricating fatty acid (FFA) and glycerol triacetate (GTA). Therein, unsaturated fatty acid is simultaneously processed through addition acetoxylation to obtain stabilized acetoxy fatty acid (AFFA). After, HOAc is recycled through vacuuming. Then, the product and the IL are stratified. The product at upper layer is taken out. The IL at lower layer can be recycled for processing transacylation and addition acetoxylation repeatedly. Therein, fatty acids including the stabilized AFFA are obtained from the product after taking out GTA through vacuum distillation.
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Page/Page column 5
(2017/03/28)
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- Method for preparing beta-ionone from modified acidic functionalized ionic liquid
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The invention relates to a method for preparing beta-ionone from modified acidic functionalized ionic liquid. The method includes the following steps that the modified acidic functionalized ionic liquid serves as a catalyst, and pseudo ionone is cyclized into beta-ionone. The modified acidic functionalized ionic liquid serves as the catalyst, the high reactive transformation rate and beta-ionone yield are achieved, the reactive transformation rate reaches 99% or above, and the beta-ionone yield reaches 94% or above. The catalyst can still keep the high transformation rate and yield after being separated and applied mechanically multiple times, the reactive transformation rate still reaches 99% or above, and the reaction yield is still kept at 90% or above.
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Paragraph 0034; 0035; 0036; 0037; 0038; 0039
(2017/09/23)
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- Based on dehydrogenation rosinyl compounds and methods for their preparation and use
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The invention discloses a compound based on dehydroabietic acid radical, a preparation method thereof and application thereof. The structure of the compound based on dehydroabietic acid radical is shown as the general formula (I), when R in the general formula (I) is H, the compound is prepared through reaction of dehydroabietic acid and raw material 1, when R in the general formula (I) is (CH2)3SO3H, the preparation method of the compound is that firstly an intermediate is prepared through reaction of 1,3-propane sultone and the raw material 1, dehydroabietic acid is then added for reaction, and the compound is obtained through extraction and filtration. The compound based on dehydroabietic acid radical is an ionic compound, is easy in preparation method, and can serve as polymerization catalysts of rosin, turpentine or pinene.
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Paragraph 0119
(2016/10/20)
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- Direct oxidative amidation of aldehydes with amines catalyzed by heteropolyanion-based ionic liquids under solvent-free conditions via a dual-catalysis process
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A simple and efficient procedure for the synthesis of amides directly from aldehydes and amines catalyzed by heteropolyanion-based ionic liquids under solvent-free conditions has been reported. The practical protocol was found to tolerate a wide range of substrates with different functional groups. Moderate to excellent yields, solvent-free media, and operational simplicity are the main highlights. The proposed dual-catalysis mechanistic pathway was briefly investigated. Furthermore, the heteropolyanion-based ionic liquids were easily reusable for this oxidative amidation.
- Fu, Renzhong,Yang, Yang,Zhang, Jin,Shao, Jintao,Xia, Xuming,Ma, Yunsheng,Yuan, Rongxin
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p. 1784 - 1793
(2016/02/10)
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- An efficient, eco-friendly and sustainable tandem oxidative amidation of alcohols with amines catalyzed by heteropolyanion-based ionic liquids via a bifunctional catalysis process
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An efficient, eco-friendly and sustainable method for the tandem oxidative amidation of alcohols with amines has been reported. Using heteropolyanion-based ionic liquids as the catalyst and tert-butyl hydroperoxide as the oxidant, this amidation reaction is operationally straightforward and provides a series of primary, secondary and tertiary amides derivatives in moderate to good yields. Solvent-free media, microwave-promoted conditions and reusability of catalysts are the main highlights. Further, the proposed bifunctional catalysis mechanistic pathway has been briefly investigated in this report.
- Fu, Renzhong,Yang, Yang,Feng, Wei,Ge, Qiuxia,Feng, Yan,Zeng, Xiaojun,Chai, Wen,Yi, Jun,Yuan, Rongxin
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p. 8319 - 8326
(2016/12/02)
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- A pyridine ionic liquid catalyzed glycerin liquid phase dehydration method of preparation of acrolein
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The present invention relates to the field of organic chemistry, particularly to a method for preparing acrolein through catalysis of glycerol liquid phase dehydration by using a pyridine ion liquid. According to the method, a pyridine ion liquid is adopted, a semi-batch reaction is adopted, and glycerol liquid phase dehydration is performed at a reaction temperature of 250-350 DEG C and a molar ratio of the ion liquid to the glycerol of 0.5:100-1.2:100 to prepare the acrolein, wherein a glycerol conversion rate is 100%, and an acrolein yield is 32.0-67.9%. According to the present invention, the biomass glycerol is adopted to prepare the high added value acrolein, raw material cost is low, raw material sources are wide, acidity of the catalyst can be adjusted, catalytic activity is high, and the process has characteristics of fast reaction, high selectivity, simple product system separation, safe and environmental protection process, and industrial production.
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Paragraph 0032; 0033
(2017/01/09)
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- Room temperature deep eutectic solvents of (1S)-(+)-10-camphorsulfonic acid and sulfobetaines: Hydrogen bond-based mixtures with low ionicity and structure-dependent toxicity
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Twelve novel deep eutectic solvents (DESs) were prepared and characterized in this work. They are mixtures of (1S)-(+)-10-camphorsulfonic acid (CSA) and differently structured sulfobetaines (SBs) with aliphatic, aromatic and amphiphilic moieties. They are liquids at room temperature, their melting points span, in fact, from -5° to 19 °C, so we can name these mixtures RTDESs (room temperature deep eutectic solvents). These zwitterionic DESs were characterized in terms of their viscosity, conductivity (and therefore ionicity via Walden plots), density, surface tension and toxicity on eukaryotic model cells. The collected data suggest that the interaction between CSA and the SBs can be ascribed as a hydrogen bond instead of a proton transfer, therefore they are not ionic liquids. To our knowledge, their position on the Walden plot, in the left portion close to the diagonal, has not yet been observed for other DESs or ionic liquid systems and indicates the low ionicity of these mixtures. A FTIR-based bioassay was performed to determine the toxicity of these mixtures on eukaryotic model cells (Saccharomyces cerevisiae). The DESs showed merely a dehydrating effect on the cells, similar to that produced by CaCl2, a low cell toxicity salt. This supports these DESs as promising green media. Amphiphilic SBs DESs showed a stronger effect on the cells and a structure-activity trend can be described for this class. A preliminary study on the use of these novel DESs as Bronsted catalyst media was accomplished by the use of one of them in chalcone synthesis, which showed promising catalytic and recycling capabilities.
- Cardellini, Fabio,Germani, Raimondo,Cardinali, Gianluigi,Corte, Laura,Roscini, Luca,Spreti, Nicoletta,Tiecco, Matteo
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p. 31772 - 31786
(2015/04/22)
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- Microwave-promoted direct amidation of unactivated esters catalyzed by heteropolyanion-based ionic liquids under solvent-free conditions
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Abstract A simple and efficient procedure for the synthesis of amides directly from unactivated esters and amines catalyzed by heteropolyanion-based ionic liquids under microwave-promoted and solvent-free conditions has been reported. The practical protocol was found to be compatible with different structurally diverse substrates. Moderate to excellent yields, solvent-free media, and operational simplicity are the main highlights. Furthermore, the heteropolyanion-based ionic liquids were easily reusable for this amidation.
- Fu, Renzhong,Yang, Yang,Ma, Yunsheng,Yang, Fei,Li, Jingjing,Chai, Wen,Wang, Quan,Yuan, Rongxin
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supporting information
p. 4527 - 4531
(2015/06/30)
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- An eco-benign and highly efficient procedure for N-acylation catalyzed by heteropolyanion-based ionic liquids using carboxylic acid under solvent-free conditions
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An eco-benign and highly efficient route for N-acylation of amines has been developed by treating amines with corresponding carboxylic acids in the presence of 2 mol % of heteropolyanion-based ionic liquids as catalysts under solvent-free conditions. This practical reaction could tolerate a wide range of substrates. Thus, various N-acylation products including N-acyl α-amino acid derivatives were obtained in moderate to excellent yields at 70 C to 120 C. Moreover, recycling studies revealed that heteropolyanion-based ionic liquids were easily reusable for this N-acylation. This method provides a green and much improved protocol over the existing methods.
- Chen, Zhikai,Fu, Renzhong,Chai, Wen,Zheng, Hao,Sun, Lin,Lu, Qiang,Yuan, Rongxin
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p. 2237 - 2245
(2014/03/21)
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- Microwave-assisted heteropolyanion-based ionic liquids catalyzed transamidation of non-activated carboxamides with amines under solvent-free conditions
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An environmentally benign and highly efficient protocol for the transamidation of non-activated carboxamides with amines using heteropolyanion-based ionic liquids as catalysts under microwave-assisted and solvent-free conditions has been developed. As evaluated by the reactions of a structurally diverse set of amides and amines, the scope and utility of the transamidation proved to be quite general. Operational simplicity, solvent-free media, the potential reusability of catalysts and wide functional group tolerance are attractive features. This method provides a much improved protocol over the existing methods.
- Fu, Renzhong,Yang, Yang,Chen, Zhikai,Lai, Wenchen,Ma, Yongfeng,Wang, Quan,Yuan, Rongxin
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p. 9492 - 9499
(2015/03/04)
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- Bronsted acidic ionic liquids catalyze the high-yield production of diphenolic acid/esters from renewable levulinic acid
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The high-yielding synthesis of diphenolic acid (DPA) using Bronsted acidic ionic liquids (BAILs) has been demonstrated in this study. Importantly, p,p′-DPA was obtained as the preferential product over o,p′-DPA with an isomer ratio over 100. Moreover, diphenolic esters were also prepared in high yield through a one-pot method.
- Liu, Hai-Feng,Zeng, Fan-Xin,Deng, Li,Liao, Bing,Pang, Hao,Guo, Qing-Xiang
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supporting information
p. 81 - 84
(2013/02/26)
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- Organic-inorganic polyoxometalate based salts as thermoregulated phase-separable catalysts for selective oxidation of thioethers and thiophenes and deep desulfurization of model fuels
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Synthesis of various organic-inorganic polyoxometalate based salts composed of sulfonated pyridinum cations and the Keggin tungstophosphate anion (PW 12O403-) and their subsequent application in the oxidation of methyl phenyl sulfide with hydrogen peroxide in aqueous media was reported. Special attention was paid to the temperature-dependent solubility of the salts as a function of the organic cation in water. Cyclic voltammetry was further used for the investigation of the redox behavior of these catalysts. Based on these properties, a novel thermoregulated phase-separable catalyst was introduced and successfully used for the selective oxidation of thioethers and thiophenes to the corresponding sulfoxides or sulfones. Catalytic oxidation of the sulfur-containing model oil (methyl phenyl sulfide, dibenzothiophene and thiophene) was also studied under optimized conditions. In both cases, excellent conversion and selectivity were obtained in relatively short reaction times. This novel catalyst showed the characteristic of homogeneous reaction at ambient temperatures and phase-separation at lower temperatures. By simple decantation, the catalyst could be easily separated from the products upon cooling of the reaction mixture and could be reused several times with high recycling efficiency.
- Rafiee, Ezzat,Eavani, Sara
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- Microwave assisted sulfopropylation of N-heterocycles using 1,3-propane sultone
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Dramatic rate acceleration was observed for N-sulfopropylation of heterocyclic compounds (1a-h) using 1,3-propane sultone(2) under microwave irradiation affording the N-sulfopropylated compounds (3a-h) in 68-95% yield.
- Adamczyk, Maciej,Rege, Sushil
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p. 9587 - 9588
(2007/10/03)
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- Dielectric Increments, Intercharge Distances and Conformation of Quaternary Ammonioalkylsulfonates and Alkoxydicyanoethenolates in Aqueous and Trifluoroethanol Solutions
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ω-(Triethylammonio)alkane-α-sulfonates (H5C2)3N+-(CH2)n-SO3- (n=2-4), pyridinio-, 2,6-lutidinio- and N-methylimidazolinio-propanesulfonates , and triethylammonioalkoxydicyanoethenolates (H5C2)3N+-(CH2)n-O-CO-C-(CN)2 (n=2, 3) have been studied by dielectric measurements (1 MHz-1 GHz) in dilute aqueous or trifluoroethanol solution.Their interchange distances have been derived from their dipole moments (μ in the range 18-30 D) calculated according to Buckingham's theory, and compared with the maximum and minimum intercharge distances estimated by molecular mechanics for the ideal fully extended and ion-pair conformations respectively.For identical tether length, stronger charge delocalization in the cationic (imidazolinium versus pyridinium) or anionic (dicyanoethenolate versus sulfonate) sites slightly increases the interchange distance, while better specific solvation of the zwitterions by hydrogen bonding in the less dissociating trifluoroethanol does not result in any significant conformational change with respect to aqueous solutions.Folding of the intercharge arm, negligible for 2-(triethylammonio)ethane-1-sulfonate, progressively increases with its length, but the ion-pair conformation, where the interchange distance becomes rapidly intensive to the tether length, is never reached.This behaviour is in good agreement with the variations of the apparent ΔpKa values of the zwitterions (normalized to that of n-C4H9SO3H) measured by potentiometry in acetic anhydride-acetic acid (9:1, v/v) solution.
- Galin, Monique,Chapoton, Alain,Galin, Jean-Claude
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p. 545 - 553
(2007/10/02)
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- Action des dihydro-4,5 oxazoles-1,3 sur le dioxy-2,2 oxathiolane-1,2 I. Synthese et caracterisations du (methyl-2 oxazolinium-1,3)-3 propanesulfonate
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The reaction of 2-methyl-1,3-oxazoline and 1-(3)propanesultone gives an ionic compound which is characterized by spectroscopic means.The proposed structure is supported by its chemical properties.
- Forestiere, A.,Sillion, B.
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p. 1381 - 1383
(2007/10/02)
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