Olefin oligomerization via new and efficient Bronsted acidic ionic liquid catalyst systems

Olefin oligomerization reaction catalyzed by new catalyst systems（a Br？nsted‐acidic ionic liquid as the main catalyst and tricaprylylmethylammonium chloride as the co‐catalyst） has been investigat‐ed. The synthesized Br？nsted acidic ionic liquids were characterized by Fourier transform infrared spectroscopy（FT‐IR）, ultraviolet‐visible spectroscopy（UV）, ^1H nuclear magnetic resonance（NMR）, and ^13 C NMR to analyze their structures and acidities. The influence of different ionic liquids, ionic liquid loading, different co‐catalysts, catalyst ratios（mole ratio of ionic liquid to co‐catalyst）, reac‐tion time, pressure, temperature, solvent, source of reactants, and the recycling of catalyst systems was studied. Among the synthesized ionic liquids, 1‐（4‐sulfonic acid）butyl‐3‐hexylimidazolium hydrogen sulfate（[HIMBs]HSO4） exhibited the best catalytic activity under the tested reaction con‐ditions. The conversion of isobutene and selectivity of trimers were 83.21% and 35.80%, respec‐tively, at the optimum reaction conditions. Furthermore, the catalyst system can be easily separated and reused; a feasible reaction mechanism is proposed on the basis of the distribution of experi‐mental products.

Application of Bronsted acid ionic liquids as green catalyst in the synthesis of 2-propanol with reactive distillation

Five Br?nsted acidic ionic liquids(ILs) were prepared and characterized by FT-IR,~1H NMR and ^(13)C NMR. Their catalytic activities for the synthesis of 2-propanol(IPOH) via transesterification of isopropyl acetate(IPAc) with methanol(Me OH) were investigated. Among all the tested ILs, [Ps-mim]HSO_4 performed best and was used as catalyst for further studies. The reaction kinetics were carried out to correlate the parameters in a homogeneous second order kinetic model. It has been found that there is close agreement between the calculated and experimental values. The high-pressure batch reactive distillation experimental apparatus was set up in order to enhance the conversion of IPAc. A high conversion of IPAc of 99.4% was obtained under the optimal reaction conditions. The catalyst [Ps-mim]HSO_4 can be recycled easily by a rotary evaporator and reused without any further treatment. The catalyst had been repeatedly used for four times and no obvious changes in the structure of catalyst could be observed.

Facile Aldol Reaction Between Unmodified Aldehydes and Ketones in Bronsted Acid Ionic Liquids

A series of condensation reactions of unmodified ketones and aromatic aldehydes to prepare α,β-unsaturated carbonyl compounds by means of Aldol reactions in Bronsted acid ionic liquids（BAILs）was explored.1-Butyl-3-methylimidazolium hydrogen sulphate（BMImHSO4）acting as an effective media and catalyst in aldol reactions was compared with other BAILs,with the advantages of high conversion and selectivity.The product was easily isolated and the left ionic liquid can be readily recovered and reused at least 3 times with almost the same efficiency.The scope and limitation of the present method were explored and the possible catalytic mechanism was speculated.

Low Environmental Load Process for the Beckmann Rearrangement of Cycloalkanone Oximes by Bronsted Acid Catalyst with Cobalt Salts

Beckmann rearrangements of oximes to lactams often require harsh conditions and/or the use of large amounts of acid catalyst. To reduce the amount of Bronsted acid required, and to avoid the formation of a large amount of undesirable byproducts under mild reaction conditions, a low environmental load process was developed. Beckmann rearrangements of cyclohexanone oxime and cyclooctanone oxime were achieved using a combination of a Bronsted acid and cobalt tetra-fluoroborate hexahydrate. Various Bronsted acid catalysts (10 - 20 mol%) were used to obtain the corresponding lactams in high yields at 80℃.

Solid Bronsted acidity boosts adsorption reactivity of nano-adsorbent for water decontamination

Despite the development of various Lewis acidic nano-adsorbents for fluoride removal through innersphere coordination,strong competition for hydroxyl ions still hinders efficient water defluoridation.In addition,the critical issue of polysilicate scaling that results from the ubiquitous silicates must be addressed.To tackle these issues,an alternative approach to enhancing adsorption reactivity by modifying nano-adsorbents with dual Lewis and Bronsted acidity is proposed.The feasibility of this approach is demonstrated by growing zirconium phosphate(ZrP)inside a gel-type anion exchanger,N201,to produce nanocomposite ZrP@N201,in which the confined ZrP contained an otherwise metastable amorphous phase with Lewis acidic Zr^(4+) sites and Bronsted acidic monohydrogen phosphate groups(-O_(3)POH).Compared with the Lewis acidic nano-zirconium oxide analog(HZ0@N201),ZrP@N201 exhibited a greatly improved adsorption capacity(117.9 vs.52.3 mg/g-Zr)and mass transfer rate(3.56×10^(-6) vs.4.55×10^(-7) cm/s),while bulk ZrP produced a thermodynamically stableα-phase with Bronsted acidity that exhibited negligible adsorption capability toward fluoride.The enhanced defluoridation activity of ZrP@N201 is attributed to Bronsted acidity and the increased outer electron density of ZA+sites,as corroborated using XPS and solid-state NMR analysis.Moreover,Bronsted acidity strengthens the resistance of ZrP@N201 to silicate,allowing its full regeneration during cyclic defluoridation.Column tests demonstrated 3-10 times the amount of clean water from(waste)for ZrP@N201 as compared to both HZO@N201 and the widely used activated aluminum oxide.This study highlights the potential of developing nano-adsorbents with dual acidities for various environmental remediation applications.

Bronsted acidic ionic liquid [C_3SO_3HDoim]HSO_4 catalyzed one-pot three-component Biginelli-type reaction: An efficient and solvent-free synthesis of pyrimidinone derivatives and its mechanistic study

A series of Bronsted acidic ionic liquids（ILs） were prepared and used for Biginelli-type condensation reaction among aromatic aldehydes, urea or thiourea and cyclopentanone. Through this reaction, the synthesis of various pyrimidinones could be achieved. Of interest, it was found that the reaction was efficiently catalyzed by a novel, eco-friendly functionalized IL [C3SO3HDoim]HSO4, which could be reused for at least 7 times without significantly loss of catalytic activity. The reaction proceeded efficiently at 80℃ to afford the desired products in good yield（up to 96%）. In addition, a possible mechanism that accounted for the IL [C3SO3HDoim]HSO4-catalyzed reaction was proposed.

Synergistic mechanism between Bronsted acid site and active cerium species in hydride transfer reaction over CeY zeolites

In this study,cyclohexene was used as a representative of olefin and catalyzed by CeY zeolites in a fixedbed reactor under mild conditions,and the influence of Ce species in hydride transfer reaction over CeY zeolites was evaluated.CeY zeolites show more excellent hydride transfer properties than HY zeolite.Based on the results of almost identical Bronsted acid properties but not the product distributions for 0.075 CeY and 0.075 CeY(DC)samples,it should be suggested that the Bronsted acid strength and density are not the deciding factors to the hydride transfer reaction.A unique band at 1442 cm^-1 in situ FTIR spectroscopy spectra are assigned to pyridine complexes bonded to a class of active Ce species that could reversibly migrate from the core of SOD cages to its 6-rings mouth towards the supercages.These results provide valuable information that these active Ce species should play a synergistic role with the Bronsted acid sites in enhancing the hydride transfer reaction with a bimolecular mechanism over CeY zeolites.

On Water： Bronsted Acidic Ionic Liquid [（CH2）4SO3HMIM][HSO4] Catalysed Synthesis of Oxindoles Derivatives

Some oxindoles derivatives are synthesized from the condensation of indoles with isatins in the presence of green and recycable catalyst [（CH2）4SO3HMIM] [HSO4] in water at room temperature.

Bronsted Acid Catalyzed gem-Difluoroallylation of Aldehydes and Ketone with β-Tosyloxy-γ,γ-difluroallylboronic Acid Pinacol Ester

A shelf-stable gem-difluorinated reagent β-tosyloxy-γ,γ-difluroallylboronic acid pinacol ester has been prepared, which can be easily used for the preparation of gem-difluorinated homoallylic alcohols through Bronsted acid （PhCO2H） catalyzed gem-difluoroallylation of aldehydes and ketone.

Mechanism of Preparation of Platform Compounds from Lignocellulosic Biomass Liquefaction Catalyzed by Bronsted Acid: A Review

Over the past two decades, research on transforming lignocellulosic biomass into small molecule chemicals byusing catalytic liquefaction has made great progress. Notably, in recent years it has been found the production of smallmolecule chemicals through directional liquefaction of lignocellulosic biomass. Understanding the liquefactionmechanism of lignocellulosic biomass is highly important. In this review, the liquefaction mechanism of lignocellulosicbiomass and model compounds of cellulose are described, and some problems and suggestions to address them aredescribed.

Surface Properties and Etherification in Microemulsion Systems of Novel Bronsted Acid Surfactants

Novel Bronsted acid-surfactants with different alkyl chains were synthesized via a two-step process, and their surface properties were studied. The critical micelle concentration（cmc）, surface tension at the cmc（γcmc）, and ability of these compounds to lower the surface tension by 0.02 N/re（C20 and pC20） were investigated at 25 and 40 ℃. The molecular architecture of the compounds strongly influenced these physicochemical parameters. The ability of these compounds to lower surface tension was found to be good. Etherification in microemulsions formed by these surfactants as well as dodecylbenzenesulfonic acid（DBSA） was performed; surfactants 3a and 3b were found to be much more efficient than dodecylbanzenesulfonic acid（DBSA）.

4-(Succinimido)-1-butane sulfonic acid as a Bronsted acid catalyst for synthesis of pyrano[4,3-b]pyran derivatives under solvent-free conditions

4-（Succinimido）-1-butane sulfonic acid as an efficient and reusable Bronsted acid catalyzed the synthesis of pyrano[4,3-b]pyran derivatives under solvent-free conditions.The catalyst can be prepared by mixing succinimide and 1,4-butanesultone that is more simple and safer than the preparation of succinimide sulfonic acid.This method has the advantages of high yield,clean reaction,simple methodology and short reaction time.The catalyst could be recycled without significant loss of activity.

Synthesis of 4,4＇-MDC in the Presence of Sulfonic Acid-functionalized Ionic Liquids

The synthesis of methylene diphenyl dimethylcarbamate （4,4＇-MDC） from methyl N-phenyl carbonate （MPC） and formaldehyde （HCHO） was conducted in the presence of sulfonic acid-functionalized ionic liquids （ILs） as dual solvent-catalyst. The influences of the kind of anion in the ionic liquids, reaction conditions and the recycle of the ionic liquid on 4,4＇-MDC synthesis reaction were investigated. In addition, the acid strength of ILs was de-termined by the Hammett method with UV-visible spectroscopy, and the acid strength-catalytic activity relationship was correlated. The activity estimation results showed that [HSO3-bmim]CF3SO3 was the optimal dual solvent-catalyst. Under the suitable reaction conditions of 70℃, 40 min, molar ratio of nMPC/nHCHO= 10/1 and mass ratio of WILs/WMPC = 4.5/1, the yield of 4,4＇-MDC based on HCHO was 89.9 % and the selectivity of 4,4＇-MDC with respect to MPC was 74.9%. Besides, [HSO3-bmim]CF3SO3 was reused four times after being purified and no significant loss in the catalytic activity was observed.

HZSM-35 zeolite catalyzed aldol condensation reaction to prepare acrylic acid and its ester:Effect of its acidic property

Acrylic acid(AA)and its ester,methyl acrylate(MA),were produced by a green one‐step aldol condensation reaction of dimethoxymethane and methyl acetate.The reaction was conducted over ZSM‐35 zeolites with different concentrations of Bronsted acid,which were prepared by the sodium ion‐exchange process with H‐form zeolite.The acidic property of HZSM‐35 was studied in detail through infrared experiments.About 51%of all bridging OH groups were distributed in cages,while 23%and 26%,respectively,were distributed in 10‐and 8‐ring channels.The catalytic performance was enhanced by a high concentration of Bronsted acid,indicating that Bronsted acid is an active site for the aldol condensation reaction.The ZSM‐35 zeolite possessing a concentration of Bronsted acid as high as 0.049 mmol/g demonstrated excellent performance with a MA+AA selectivity of up to 73%.

Catalysis performance comparison of a Br?nsted acid H_2SO_4 and a Lewis acid Al_2(SO_4)_3 in methyl levulinate production from biomass carbohydrates

An experimental investigation was conducted to understand the roles of the Br？nsted acid H2SO4 and Lewis acid Al2（SO4）3 in methyl levulinate（ML） production from biomass carbohydrates, including glucose,fructose and cellulose. The product distributions with different catalysts revealed that the Lewis acid was responsible for the isomerization of methyl glucoside（MG）, producing a significant amount of the subsequent product 5-methoxymethylfurfural（MMF）, while the Br？nsted acid facilitated the production of ML from MMF. Al2（SO4）3 was efficient for monosaccharide conversion but not for cellulose. Using ball-milled cellulose with Al2（SO4）3 resulted in a desired ML yield within a reasonable reaction time. The significant catalysis performances of two types of acids will guide the design of efficient catalytic processes for the selective conversion of biomass into levulinate esters.

Br?nsted acid catalyzed addition of N^1-p-methyl toluenesulfonyl triazole to olefins for the preparation of N^2-alkyl 1,2,3-triazoles with high N^2-selectivity

An efficient new method has been developed to synthesize N2‐alkyl 1,2,3‐triazole products by tol‐uenesulfonic acid （TsOH） catalyzed addition of N1‐Ts substituted 1,2,3‐triazoles to olefins. The reac‐tions of monosubstituted and unsubstituted triazole substrates with various olefins, including vinyl esters, are explored.

Preparation of ZSM-5 containing vanadium and Br?nsted acid sites with high promoting of styrene oxidation using 30% H_2O_2

Design and synthesis of low cost and efficacious industrial catalyst for the oxidation of styrene has been an important research project.Herein,ZSM-5 zeolite containing tetrahedral vanadium(V)and Br?nsted acid sites(V-H-ZSM-5)was prepared,and identified by characterizations such as XRD,SEM,UV–vis,NH3-TPD,H2-TPR N2-adsorption/desorption and FTIR.V-H-ZSM-5 performed extremely enhanced catalytic activity for the oxidation of styrene with 30%H2O2 at 40°C.Moreover,in-situ FTIR spectrum was used to investigate the catalytic mechanism.The results demonstrate that Br?nsted acid site could not only increase the adsorption concentration of styrene in the micropores of V-H-ZSM-5 via theπcomplex interaction between double bond of styrene and Br?nsted acid sites,but also increase the oxidation potential of H2O2.The synergetic action of tetrahedral vanadium(V)and Br?nsted acid enhanced the catalytic activity for the oxidation of styrene with 30%H2O2.Impressively,V-H-ZSM-5 performed high reusability within five runs at a low reaction temperature(40°C)for the first time.

Br?nsted acidic ionic liquid catalyzed synthesis of benzo[a]carbazole from renewable acetol and 2-phenylindoles in a biphasic system

An efficient metal-free strategy for the synthesis of pharmaceutically relevant benzo[α]carbazoles from the derivatives of readily available 2-phenylindole and bio-renewable acetol in an aqueous biphasic system was developed. This protocol employed a sulfone-containing Bronsted acidic ionic liquid as the catalyst, which could be used for five times without a noticeable decrease in its activity and selectivity. Various substituted 2-phenylindoles and α-hydroxyketones participated in the reaction smoothly, with water as the sole byproduct. Mechanistically, the reaction involved the conventional carbon-nucleophile-induced Heyns-type rearrangement and downstream intramolecular olefination.

BrФnsted Acidic Ionic Liquids: Novel Efficient, Cost-effective and Reusable Solvent-catalysts for Ritter Reaction

Several Bronsted acidic ionic liquids（ILs） were synthesized and used as dual solvent-catalysts for the Ritter reaction of benzonitrile with tert-butanol. In particular, IL11（[NSPTEA][OTF]） showed excellent catalytic activity for the Ritter reaction. In the presence of IL11, various nitriles and tertiary alcohols as well as secondary alcohols were converted smoothly to the corresponding amides in good to excellent yields. In addition, this cost-effective ionic liquid [NSPTEA][OTF] was easily separated from the reaction mixture by extraction with a small amount of water, and was recycled five times without any significant loss in activity.

Brφsted-acidic ionic liquids as efficient catalysts for the synthesis of polyoxymethylene dialkyl ethers

Acetalation of formaldehyde(HCHO)with dialkyl formal or aliphatic alcohol to prepare polyoxymethylene dialkyl ethers(RO(CH2O)nR,n≥1)catalyzed by Br?nsted‐acidic ionic liquids has been developed.The correlation between the structure and acidity activity of various ionic liquids was studied.Among the ionic liquids investigated,1‐(4‐sulfonic acid)butyl‐3‐methylimidazolium hydrogen sulfate([MIMBs]HSO4)exhibited the best catalytic performance in the reaction of diethoxymethane(DEM1)with trioxane.The influences of ionic liquid loading,molar ratio of DEM1to HCHO,reaction temperature,pressure,time,and reactant source on the catalytic reaction were explored using[MIMBs]HSO4as the catalyst.Under the optimal conditions of n([MIMBs]HSO4):n(DEM1):n(HCHO)=1:80:80,140°C,and4h,the conversion of HCHO and selectivity for DEM2?8were92.6%and95.1%,respectively.The[MIMBs]HSO4catalyst could be easily separated and reused.A feasible mechanism for the catalytic performance of[MIMBs]HSO4was proposed.