Glycerol functionalized imidazolium tri-cationic room temperature ionic liquids: Synthesis, properties and catalytic performance for 2-azidoalcohol synthesis from epoxide

Chaugule, A.A.,Tamboli, A.H.,Sheikh, F.A.,Chung, W.J.,Kim, H. Elsevier 2015 Journal of molecular liquids Vol.208 No.-

Imidazolium based tri-cationic room temperature ionic liquid (RTILs) were synthesized and characterized, and their physicochemical properties such as thermal stability, viscosities and solubility were investigated. These ionic liquids exhibited excellent catalytic activity for 2-azidoalcohol synthesis from epoxide and sodium azide. The present tri-cationic RTILs/water catalytic systems showed better catalytic performance than their mono-cationic counterparts. Among all prepared ionic liquids, [GLY(mim)<SUB>3</SUB>][OMs] gave best results with up to 96% yield of 2-azidoalcohol. The reusability test of glycerol-tri (3-methylimidazolium) trimesylate [GLY(mim)<SUB>3</SUB>][OMs]<SUB>3</SUB> were studied for five consecutive cycles presenting the highest yield without loss in their catalytic activity. Hence, the experimental results demonstrated that structural variation of synthesized tri-cationic RTILs can dictate their physicochemical and catalytic activities.

CuCl₂@Poly-IL catalyzed carboxylation of terminal alkynes through CO₂ utilization

Chaugule, Avinash A.,Tamboli, Ashif H.,Kim, Hern Elsevier 2017 CHEMICAL ENGINEERING JOURNAL -LAUSANNE- Vol.326 No.-

<P><B>Abstract</B></P> <P>The carboxylation of terminal alkynes from CO<SUB>2</SUB> is a most attractive route in green chemistry point of view. Herein, we synthesized a novel CuCl<SUB>2</SUB>@Poly-GLY(1-Vim)<SUB>3</SUB>(OMs)<SUB>3</SUB> catalyst and employed to the efficient carboxylation of terminal alkynes (phenyl carboxylate esters) by utilizing CO<SUB>2</SUB> under 4MPa, at 40°C. In presence of catalyst, various terminal alkynes found to be easily reacting with CO<SUB>2</SUB> and organic halide to affording a high yield of carboxylic ester. Moreover, CuCl<SUB>2</SUB>@Poly-GLY(1-vim)<SUB>3</SUB>(OMs)<SUB>3</SUB> catalyst is capable to obtain a high yield of corresponding carboxylic ester using various types organic halide. Furthermore, CuCl<SUB>2</SUB>@Poly-GLY(1-vim)<SUB>3</SUB>(OMs)<SUB>3</SUB> catalyst able to easily recover and reuse for four times without any obvious loss in catalytic activity. The catalytic reactivity of CuCl<SUB>2</SUB>@Poly-GLY(1-vim)<SUB>3</SUB>(OMs)<SUB>3</SUB> catalyst is explained on the basis of predicted mechanism.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Preparation of Poly-GLY(mim)<SUB>3</SUB>(OMs)<SUB>3</SUB>. </LI> <LI> Synthesis of Cu@Poly-GLY(mim)<SUB>3</SUB>(OMs)<SUB>3</SUB> catalyst. </LI> <LI> Efficient carboxylation of terminal alkyne. </LI> <LI> Catalyst able to reuse for four times. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Ionic liquid based Cu₂S@C catalyst for effective coupling of diaryl diselenide with aryl halides under ligand-free conditions

Chaugule, Avinash A.,Pawar, Atul A.,Tamboli, Ashif H.,Bandal, Harshad A.,Chung, Wook-Jin,Kim, Hern Elsevier 2018 CHEMICAL ENGINEERING JOURNAL -LAUSANNE- Vol.351 No.-

<P><B>Abstract</B></P> <P>Diaryl selenide is the main drug candidate today. An efficient, easy and ligand free cross-coupling reaction of aryl halide and diaryl diselenide was carried out by as-prepared copper sulfide functionalized carbon (Cu<SUB>2</SUB>S@C) catalyst. Cu<SUB>2</SUB>S@C catalyst was developed using novel tri-cationic ionic liquid (IL) as a precursor and sulfur source. Catalyst found to having rich content of heteroatoms (S and N) by EDX and Elemental mapping characterization techniques. Effective utilization of catalyst was carried out by synthesis of variety of aryl selenide in excellent yield from readily halides and diaryl diselenides. Active centers in the catalyst provide efficient activation for crosscoupling reaction. Moreover, catalyst where easily reusable for three times without any obvious loss in catalytic activity.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Preparation of Poly-GLY(1-vinyl)<SUB>3</SUB>(OMs)<SUB>3</SUB>. </LI> <LI> Synthesis of Cu<SUB>2</SUB>S@C catalyst. </LI> <LI> Efficient synthesis of aryl selenide. </LI> <LI> Catalyst able to reuse for three times. </LI> </UL> </P>

Ionic liquid as a catalyst for utilization of carbon dioxide to production of linear and cyclic carbonate

Chaugule, Avinash A.,Tamboli, Ashif H.,Kim, Hern Elsevier 2017 Fuel Vol.200 No.-

<P><B>Abstract</B></P> <P>In this review, primary focus on the ionic liquid (IL) catalysts and related catalytic systems for utilization of carbon dioxide to a production of linear as well as cyclic carbonate, and describes the innovative progress observed during last ten years. This review covers trend of various catalysts starting from first conventional ILs (tetrabutylammonium bromide and imidazolium IL) to the latest metal containing IL systems employed for the efficient production of dimethyl carbonate. Moreover, recent advances in DMC production also summarizes using the catalysts which contain novel super base facilitated tri-cationic IL systems. Similarly, cyclic carbonate synthesis reveals the benefits of using IL based catalyst on the verity of different supporting materials such as alumina, silica, carbon nanotubes, magnetic nanoparticles, poly(ethylene glycol), polystyrene, cellulose, and chitosan. The summary of ammonium, phosphonium and both functionalized and unfunctionalized imidazolium salts indicates that the turnover frequency for epoxide and propylene oxide enhances under mild reaction condition. Overall, it is clear that metal ions or super base in the combination of ILs can improve the conversions and the presence of hydroxyl, carboxyl, and other functional groups will enhance the yield multiple folds through hydrogen bonding interaction.</P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Glycerol functionalized imidazolium tricationic room temperature ionic liquids synthesis and application for 2-azidoalcohol synthesis from epoxide

( Avinash Chaugule ),( Ashif Tamboli ),김헌 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.1

The new tricationic room temperature ionic liquids (RTILs) based on 3-methylimidazolium were synthesized form glycerol. The RTILs presented interesting physicochemical properties at different temperature. The Lewis acidity of prepared ionic liquid was determined by IR spectroscopy. The [GLY(mim)₃][OMs] IL showed highest Lewis acidic behavior. The catalytic activity and reusability of these tricationic RTILs were investigated for 2-azidoalcohol synthesis from epoxide and sodium azide. The prepared tricationic RTILs in presence of water as proton source exhibited high catalytic activity compared to monotri-cationc ILs.

Highly efficient synthesis of dimethyl carbonate from methanol and carbon dioxide using metal oxy chloride/hydroxyl ionic Liquid as a trifunctional catalytic system

( Avinash Chaugule ),김헌 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.0

Dimethyl carbonate (DMC) was synthesized in excellent yield by direct physically or chemically adsorption of carbon dioxide on [EmimOH][NTf2] IL in presence of SmOCl and super base. Meaningfully, novel ternary catalyst system was found to display noticeable conversion of methanol (13.01%) with excellent selectivity (99.13%) towards DMC. The interaction of CO2 with IL in presence of superbase was discussed by FT-IR and 13C characterization as well as catalytic reactivity was proved by predictable mechanism. Various conditions such as reaction temperature, pressure and time were investigated for DMC.

Synthesis of Ce-Ni based nanofiber as novel catalyst for hydrogen production from sodium borohydride hydrolysis

( Ashif Tamboli ),( Avinash Chaugule ),김헌 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.1

The cerium-nickel loaded on titanium nanofibers were fabricated by simple electrospinning technique for hydrogen production. The catalytic activity of derived composite oxides after calcinations was studied at different parametric conditions. The prepared nanofibers were characterized by the SEM, EDX, FTIR, XRD, BET and TEM technique. The catalytic activities results showed that the activity of catalyst is due to the synergic affect of cerium and nickel composite oxide. The activation energy and recycling ability of prepared nanofiber was evident a beneficial effect of cerium in the catalytic activity for hydrogen production.

Catalytic developments in the direct dimethyl carbonate synthesis from carbon dioxide and methanol

Tamboli, Ashif H.,Chaugule, Avinash A.,Kim, Hern Elsevier 2017 Chemical Engineering Journal Vol.323 No.-

<P><B>Abstract</B></P> <P>The present review compiles the recently published literature for the single step dimethyl carbonate (DMC) synthesis from carbon dioxide (CO<SUB>2</SUB>) and methanol. The various routes of DMC synthesis are also discussed in short with their advantages and disadvantages in order to distinguish the merits of direct DMC synthesis route. Next, the major applications of DMC such as in electrochemistry, as fuels additive, as solvent and building block in organic synthesis are described. The major problems in the direct DMC synthesis route such as low yield, reaction rate, thermodynamic limitations and hydrolysis of produced DMC are also pointed out. Furthermore, the significance of fabricating an effective dehydrating agent for the removal of water from the reaction is narrated for the enhancement of DMC yield. The type of catalyst materials based on their nature i.e. metal carbonates, tin-based catalysts, metal oxides, organic catalysts and polymer based materials, etc. used for title reaction are separately discussed in details. The varieties of dehydrating agents and their role in DMC production is explained with the help of most recent reported literature.</P> <P><B>Highlights</B></P> <P> <UL> <LI> DMC are commonly used as fuel additive, in electrochemistry and organic synthesis. </LI> <LI> This study presents an overview of advances in direct DMC synthesis from CO<SUB>2</SUB> and methanol. </LI> <LI> It also summarizes the challenges such as necessity of dehydrating agents. </LI> <LI> And the uses of various catalysts to address challenges like low yield and thermodynamic limitations. </LI> </UL> </P>

Highly selective and multifunctional chitosan/ionic liquids catalyst for conversion of CO₂ and methanol to dimethyl carbonates at mild reaction conditions

Tamboli, A.H.,Chaugule, A.A.,Kim, H. Butterworths [etc.] ; Elsevier Science Ltd 2016 Fuel Vol.166 No.-

The direct reaction of CO<SUB>2</SUB> and methanol is the most attractive route for dimethyl carbonates (DMC) synthesis from the point of green chemistry and sustainable development. In this work, a 10wt% chitosan/ionic liquid (IL)-catalyst system having hydroxyl and amine groups as nucleophilic and carbon dioxide absorption sites was synthesized for DMC synthesis. This method provides an example of how an abundant biopolymer can be dissolved in IL for direct use as an electron-rich amino or hydroxyl group source for CO<SUB>2</SUB> capture, which extends the scope of efficient DMC synthesis. The catalyst was characterized by Wide Angle X-ray diffraction (WAXRD) to confirm the structural distortion of crystalline chitosan where resultant active groups will be available for CO<SUB>2</SUB> absorption. The catalyst showed excellent catalytic activity, selectivity and stability under mild conditions: 16.90% methanol conversion and ~98.72% DMC selectivity. The catalytic performance revealed that the as-prepared ''green'' catalyst is very active and reusable for the DMC synthesis.

Chitosan grafted polymer matrix/ZnCl₂/1,8-diazabicycloundec-7-ene catalytic system for efficient catalytic fixation of CO₂ into valuable fuel additives

Tamboli, A.H.,Chaugule, A.A.,Kim, H. Butterworths [etc.] ; Elsevier Science Ltd 2016 Fuel Vol.184 No.-

The chitosan grafted polymer matrix/ZnCl<SUB>2</SUB>/1,8-diazabicycloundec-7-ene (DBU) novel catalytic system was developed. It was found out that the microwave assisted technique was efficient for chitosan grafting compared to conventional chemical method. The morphology, thermal stability, functional groups, crystalline nature of grafted polymer matrix were investigated using scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR) and wide angle X-ray diffraction (WAXRD) techniques, respectively. SEM images revealed that the surface of chitosan became rough and cross-linked after grafting with amine derivatives. The prepared sorbent showed good CO<SUB>2</SUB> absorption capacity i.e. ~0.35mmol/g-catalyst, due to the presence of amines and hydroxyl CO<SUB>2</SUB> philic functional groups which shows an obvious positive effect on its CO<SUB>2</SUB> capture capacity. These properties enable this sorbent to be a promising catalyst for dimethyl carbonate (DMC) synthesis from methanol and CO<SUB>2</SUB>. DBU was used as a super base for methanol activation by abstracting acidic proton and ZnCl<SUB>2</SUB> for the activation of CO<SUB>2</SUB>. Remarkably, the excellent methanol conversion up to ~23% and ~99% DMC selectivity were achieved by Ch-g-PEI/ZnCl<SUB>2</SUB>/DBU catalysts system at ambient reaction conditions. Catalytic synthesis of organic carbonates is of significant interest both conceptually and practically because this can produce compounds from CO<SUB>2</SUB>. This synthesis can provide mild alternative approaches to the direct conversion of CO<SUB>2</SUB> to organic carbonates, an important fuel and building block for organic synthesis.