01938nas a2200145   4500008004100000245008500041210006900126260000800195300001400203490000700217520140800224100001801632700002501650856011701675       2017                        eng d00aCascade reductive etherification of bioderived aldehydes over Zr-based catalysts0 aCascade reductive etherification of bioderived aldehydes over Zr  cOCT  a4090-41010 v103 aAn efficient one-pot catalytic cascade sequence has been developed for the production of value-added ethers from bioderived aldehydes. Etherification of 5-(hydroxymethyl)furfural with different aliphatic alcohols over acidic Zr-montmorillonite (Zr-Mont) catalyst produced a mixture of 5-(alkoxymethyl)furfural and 2-(dialkoxymethyl)-5-(alkoxymethyl)furan. The latter was selectively converted back into 5-(alkoxymethyl)furfural by treating it with water over the same catalyst. The synthesis of 2,5-bis(alkoxymethyl)furan was achieved through a cascade sequence involving etherification, transfer hydrogenation, and re-etherification over a combination of acidic Zr-Mont and the charge-transfer hydrogenation catalyst [ZrO(OH)(2)]. This catalyst combination was further explored for the cascade conversion of 2-furfuraldehyde into 2-(alkoxymethyl)furan. The scope of this strategy was then extended for the reductive etherification of lignin-derived arylaldehydes to obtain the respective benzyl ethers in >80% yield. Additionally, the mixture of Zr-Mont and ZrO(OH)(2) does not undergo mutual destruction, which was proved by recycling experiments and XRD analysis. Both the catalysts were thoroughly characterized using BET, temperature-programmed desorption of NH3 and CO2, pyridine-FTIR, XRD, inductively coupled plasma optical emission spectroscopy, and X-ray photoelectron spectroscopy techniques.1 aShinde, Suhas1 aRode, Chandrashekhar  uhttps://library.ncl.res.in/content/cascade-reductive-etherification-bioderived-aldehydes-over-zr-based-catalysts02278nas a2200241   4500008004100000022001400041245009300055210006900148260000800217300001400225490000600239520147500245653003001720653002401750653001801774653003101792653001201823100001801835700002001853700002001873700002501893856011801918       2018                        eng d  a2365-654900aCascade synthesis of 5-(Acetoxymethyl) furfural from carbohydrates over Sn-mont catalyst0 aCascade synthesis of 5Acetoxymethyl furfural from carbohydrates   cAUG  a8770-87780 v33 a<p>The 5-(Acetoxymethyl)furfural (AcMF) is emerged as an important alternative for 5-(hydroxymethyl)furfural (HMF). It is also a starting material for those products which are typically prepared from HMF. The growing importance of AcMF encouraged us to prepare it directly from cheap and abundant carbohydrates. The production AcMF from glucose and glucose-like carbohydrates is an exigent assignment, owing to tough isomerisation of glucose to fructose. The Sn-Mont catalyst having a unique combination of Lewis as well as Bronsted acid sites was employed for direct glucose conversion into AcMF. Lewis acid sites of Sn-Mont facilitate the isomerisation of glucose to fructose. At the same time, dehydrative-esterification of fructose to AcMF is catalyzed by Bronsted acid sites of Sn-Mont. Different concentrations of Sn containing Sn-Mont catalysts were by prepared mixing montmorillonite clay with different molar concentration (e.g. 0.1 M-0.4 M) of aqueous solutions of SnCl4 center dot 5H(2)O. AcMF was produced in as high as 43% yield directly from glucose over Sn-Mont(0.3 M) catalyst owing to its highest acid strength. The efficacy of Sn-Mont(0.3 M) catalyst was also probed for sucrose and fructose that resulted in 53% and 58% yield of AcMF, respectively. The critical properties of all the prepared Sn-Mont catalysts were investigated through XRD, BET surface area, ICP-OES, temperature-programmed desorption of NH3 and pyridine-FTIR and XPS techniques.</p>10a5-(Acetoxymethyl)furfural10aBronsted/Lewis acid10acarbohydrates10aDehydrative-esterification10aSn-Mont1 aShinde, Suhas1 aDeval, Kashmira1 aChikate, Rajeev1 aRode, Chandrashekhar  uhttps://library.ncl.res.in/content/cascade-synthesis-5-acetoxymethyl-furfural-carbohydrates-over-sn-mont-catalyst02582nas a2200145   4500008004100000245009900041210007100140260000800211300001600219490000600235520201500241100001802256700003302274856012902307       2018                        eng d00aFriedel–crafts alkylation over Zr-mont catalyst for the production of diesel fuel precursors0 aFriedel–crafts alkylation over Zrmont catalyst for the productio  cMAY  a5491–55010 v33 aHeterogeneous Zr-Mont catalyst prepared by a simple protocol was employed for the production of diesel fuel precursors via Friedel–Crafts (FC) alkylation of petroleum-derived arenes (e.g., mesitylene, xylene, and toluene) with biomass-derived 5-(hydroxymethyl)furfural (HMF), HMF derivatives, and carbohydrates. Initially, several acidic catalysts were screened for the FC alkylation of mesitylene with HMF in nitroethane solvent. Among all, Zr-Mont catalyst gave an exceptionally high yield (80%) of mesitylmethylfurfural (MMF). The catalytic activity of Zr-Mont was also evaluated for the alkylation of different petroleum-derived arenes with ester/halogen derivatives of HMF. Suitable acid strength and high surface area of Zr-Mont were its major attributes to make it the most efficient solid acid catalyst for this FC reaction. Even after several reuses, the catalytic activity of Zr-Mont was found to be consistent, which was also evidenced by the acidity measurements of fresh and reused Zr-Mont catalysts by temperature-programmed desorption of ammonia and pyridine Fourier transform infrared spectroscopy techniques. Direct conversion of glucose to diesel fuel precursors was also attempted over Zr-Mont catalyst in mesitylene and polar nonacidic solvents at 150 °C. However, the activity of Zr-Mont catalyst was limited for glucose dehydration to HMF and MMF did not form. When the same experiment was performed in formic acid medium, MMF was produced in 34% yield. After the addition of formic acid, the reaction becomes biphasic which contains mesitylene as an organic phase and formic acid as an aqueous phase. Formic acid worked as a solvent, reactant, and cocatalyst, whereas mesitylene worked as a reactant and product extraction phase to enable easy product isolation. With this strategy, other diesel fuel precursors were also produced in 26–30% yields from glucose and different arenes. Similar strategy was successfully extended for the conversion of sucrose to diesel fuel precursors.1 aShinde, Suhas1 aRode, Chandrashekhar, Vasant  uhttps://library.ncl.res.in/content/friedel%E2%80%93crafts-alkylation-over-zr-mont-catalyst-production-diesel-fuel-precursors01424nas a2200241   4500008004100000022001400041245014100055210006900196260000900265300001000274490000800284520057700292653001300869653001300882653002900895653003200924653001500956100001800971700001800989700001901007700002501026856013101051       2019                        eng d  a1566-736700aPyridine immobilised on magnetic silica as an efficient solid base catalyst for Knoevenagel condensation of furfural with acetyl acetone0 aPyridine immobilised on magnetic silica as an efficient solid ba  cMAY   a81-850 v1243 a<p>Novel heterogeneous pyridine immobilised magnetic silica (Fe3O4@SiO2-Py) was found to be an efficient, greener and heterogeneous solid base catalyst for the Knoevenagel condensation of furfural with acetylacetone under optimized reaction conditions. The Knoevenagel condensation product 3-(2-furylmethylene)-2,4-pentanedione (FMP), a jet fuel precursor, was produced in high yield of 85% with 94% conversion of furfural at 100 degrees C within a period of 4 h. Fe3O4@SiO2-Py catalyst showed excellent stability and recyclability without losing its initial activity.</p>10afurfural10aJet fuel10aKnoevenagel condensation10aSilica immobilised pyridine10aSolid base1 aTarade, Komal1 aShinde, Suhas1 aSakate, Sachin1 aRode, Chandrashekhar  uhttps://library.ncl.res.in/content/pyridine-immobilised-magnetic-silica-efficient-solid-base-catalyst-knoevenagel-condensation03613nas a2200169   4500008004100000245012100041210006900162260000800231300001400239490000700253520299500260100001603255700001803271700001903289700000503308856013003313       2019                        eng d00aTwo-step sequence of acetalization and hydrogenation for synthesis of diesel fuel additives from furfural and diols.0 aTwostep sequence of acetalization and hydrogenation for synthesi  cAUG  a7466-74720 v333 a<p><span class="hitHilite">Acetalization</span> <span class="hitHilite">of</span> <span class="hitHilite">diols</span> with <span class="hitHilite">furfural</span> and subsequent <span class="hitHilite">hydrogenation</span> <span class="hitHilite">of</span> acetal products provided potential <span class="hitHilite">fuel</span> <span class="hitHilite">additives</span> that could be blended into commercial <span class="hitHilite">diesel</span>. Glycerol could be an interesting polyol <span class="hitHilite">for</span> <span class="hitHilite">acetalization</span> with <span class="hitHilite">furfural</span> due to its low cost, and it is produced as a byproduct in very large amount in the process <span class="hitHilite">of</span> biodiesel production. In this work, glycerol <span class="hitHilite">acetalization</span> with <span class="hitHilite">furfural</span> has been selected as a model reaction. <span class="hitHilite">Acetalization</span> reaction was performed under neat conditions (solventless) with 1:1 molar ratio <span class="hitHilite">of</span> <span class="hitHilite">furfural</span> and glycerol at room temperature over various acid catalysts, including homogeneous and heterogeneous acids. Among several catalysts, Zr-Mont, a heterogeneous solid acid having controlled acidity, gave as high as 78% isolated yield <span class="hitHilite">of</span> acetal products. Interestingly, acetal products can be isolated in pure form by performing extraction using cyclohexane that enables selective extraction <span class="hitHilite">of</span> product, and unreacted glycerol and <span class="hitHilite">furfural</span> were left in aqueous phase, which can be recycled. Further, to make <span class="hitHilite">fuel</span> components <span class="hitHilite">from</span> isolated acetal product <span class="hitHilite">of</span> glycerol and <span class="hitHilite">furfural</span>, <span class="hitHilite">hydrogenation</span> was performed over a series <span class="hitHilite">of</span> supported noble-metal catalysts under low H-2 pressure at room temperature. Among them, 5% Pd/C showed very high activity <span class="hitHilite">for</span> ring <span class="hitHilite">hydrogenation</span> that resulted in high yield <span class="hitHilite">of</span> <span class="hitHilite">hydrogenation</span> products. However, hydrogenated product contains free hydroxyl group that needs to be subsequently etherified or acetylated. Interestingly, etherified derivative was obtained in high yield compared to acetylated derivative. In addition, several other <span class="hitHilite">diols</span> were treated with <span class="hitHilite">furfural</span> and their products were subsequently hydrogenated over 5% Pd/C under very low H-2 pressure. The properties <span class="hitHilite">of</span> resulting compounds were investigated so as to find most suitable candidates as <span class="hitHilite">additives</span> to commercial <span class="hitHilite">diesel</span>.</p>
1 aPatil, Anil1 aShinde, Suhas1 aKamble, Sanjay1 a  uhttps://library.ncl.res.in/content/two-step-sequence-acetalization-and-hydrogenation-synthesis-diesel-fuel-additives-furfural02024nas a2200241   4500008004100000022001400041245011800055210006900173260000900242300001200251490000600263520120900269653003301478653001601511653001501527653002301542653001401565100001801579700001801597700001801615700002501633856012401658       2020                        eng d  a2365-654900aIntegration of heterogeneous acid and base catalysis for clean synthesis of jet-fuel precursor from carbohydrates0 aIntegration of heterogeneous acid and base catalysis for clean s  cJAN   a392-4000 v53 a<p>C-12 branched alkane fuel precursor was produced from carbohydrates using an efficient integrated solid acid and base catalysis approach involving: i) isomerisation-dehydration of carbohydrates to 5-(hydroxymethyl)furfural (HMF) over solid acid catalyst having both Lewis and Bronsted sites) in a biphasic MIBK (methylisobutylketone): water + DMSO solvent system and ii) Claisen-Schmidt condensation of crude HMF with MIBK over solid base catalyst. Initially, high yield of jet fuel precursor, (E)-1-(5-(hydroxymethyl)furan-2-yl)-5-methylhex-1-en-3-one from pure HMF and MIBK was achieved over basic CaMgAl(231) catalyst. The glucose dehydration to HMF was optimized in biphasic MIBK: H2O-NaCl: DMSO (8:1.5:0.5; v/v/v) system, with complete glucose conversion and 42% HMF yield over Zr-Mont possessing both Lewis and Bronsted acid sites. In an integrated dehydration + Claisen-Schmidt condensation sequence, Zr-Mont catalyst was filtered off and the crude HMF with MIBK underwent Claisen-Schmidt condensation over CaMgAl(231) catalyst. The overall 32% yield of Claisen-Schmidt condensation product was achieved from glucose. MIBK acting also as a product extractant, could be recovered upto 80%.</p>
10aClaisen-Schmidt condensation10adehydration10aintegrated10ajet-fuel precursor10arenewable1 aShinde, Suhas1 aTarade, Komal1 aMitra, Gaurav1 aRode, Chandrashekhar  uhttps://library.ncl.res.in/content/integration-heterogeneous-acid-and-base-catalysis-clean-synthesis-jet-fuel-precursor01997nas a2200229   4500008004100000022001400041245012500055210006900180260000800249300001100257490000800268520118700276653001901463653001801482653003301500653002401533653001701557100001801574700001801592700002501610856013201635       2020                        eng d  a0378-382000aMagnetically separable catalyst for condensation of renewable aldehydes and 2-methylfuran to saturated cyclic oxygenates0 aMagnetically separable catalyst for condensation of renewable al  cJAN  a1061910 v1973 a<p>The saturated cyclic ethers produced from biomass derived aldehydes and 2-methylfuran are the potential diesel fuel candidates. The synthesis of saturated cyclic ethers is a two step process which involves acid catalyzed condensation of aldehydes with 2-methylfuran and the subsequent selective furan ring hydrogenation of the condensation products. Here, we designed a novel recyclable magnetic solid acid catalyst such as [Fe3O4@SiO2-Pr-Py-H][2HSO(4)(2-)] and employed for the condensation of 2-methylfuran with formaldehyde as model substrates and reaction parameters were optimized. Under the set reaction conditions, condensation of 2-methylfuran with several other aldehydes were also successfully achieved with very good yields. Further, several supported noble metal catalysts were screened in order to find suitable catalyst system for selective furan ring hydrogenation of condensation products. Among those, 5% Pd/C was found to be very active and selective for furan ring hydrogenation without formation of ring opened products under very low hydrogen pressure at room temperature. Prepared catalysts were thoroughly characterized with sophisticated techniques.</p>
10afuel additives10aHydrogenation10aHydroxyalkylation-alkylation10aMagnetic solid acid10aOrganosilica1 aTarade, Komal1 aShinde, Suhas1 aRode, Chandrashekhar  uhttps://library.ncl.res.in/content/magnetically-separable-catalyst-condensation-renewable-aldehydes-and-2-methylfuran-saturated02135nas a2200253   4500008004100000022001400041245011400055210006900169260000800238300001100246490000700257520127700264653002601541653001301567653002301580653002101603100002301624700001801647700002101665700001601686700002401702700002501726856013001751       2021                        eng d  a0019-452200aRole of preparation parameters of Cu-Zn mixed oxide catalyst in solvent free glycerol carbonylation with urea0 aRole of preparation parameters of CuZn mixed oxide catalyst in s  cJUL  a1000900 v983 aSolvent-free carbonylation of glycerol with urea to glycerol carbonate (GC) was achieved over heterogeneous Cu-Zn mixed oxide catalyst. Cu-Zn catalysts with different ratios of Cu:Zn were prepared using co-precipitation (CP) and oxalate gel (OG) methods. As compared to CuO-ZnO(2:1) catalyst prepared by oxalate gel (OG) method, much higher conversion of glycerol and highest selectivity towards glycerol carbonate (GC) was achieved with CuO-ZnO_CP(2:1) catalyst. Physicochemical properties of prepared catalysts were investigated by using XRD, FT-IR, BET, TPD of CO2 and NH3 and TEM techniques. The effect of stoichiometric ratio of Cu/Zn, calcination temperature of CuO-ZnO catalysts and effect of reaction parameters such as molar ratio of substrates, time and temperature on glycerol conversion to GC were critically studied. Cu/Zn of 2:1 ratio, glycerol-urea 1:1 molar ratio, 145 degrees C reaction temperatures were found to be optimized reaction conditions to achieve highest glycerol conversion of 86% and complete selectivity towards GC. The continuous expel of NH 3 from reaction the mixture avoided formation of ammonia complex with CuO-ZnO catalyst. As a result of this, CuO-ZnO catalyst could be recycled up to three times without losing its initial activity.10aCo-precipitation (CP)10aGlycerol10aGlycerol carbonate10aOxalate gel (OG)1 aCharate, Shrinivas1 aShinde, Suhas1 aKondawar, Sharda1 aDesai, Uday1 aWadgaonkar, Prakash1 aRode, Chandrashekhar  uhttps://library.ncl.res.in/content/role-preparation-parameters-cu-zn-mixed-oxide-catalyst-solvent-free-glycerol-carbonylation