01890nas a2200241   4500008004100000022001400041245011100055210006900166260007300235300001200308490000800320520101700328653001101345653001201356653001301368653001901381653003001400653002101430100001901451700002101470700002801491856012901519       2005                        eng d  a1381-116900aCopper(II) ion-exchanged montmorillonite as catalyst for the direct addition of N-H bond to CC triple bond0 aCopperII ionexchanged montmorillonite as catalyst for the direct  aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJUL  a139-1440 v2363 a<p>An efficient synthesis of phenyl-(1-phenylethylidene)amine using copper-exchanged montmorillonite clay (Cu K-10) is demonstrated. The catalyst was characterized using UV-vis, XRD, BET surface area measurements, pyridine adsorption etc. The XRD and surface area measurement show that the structural characteristics of the support montmorillonite K-10 (K-10) are preserved after Cu exchange. The hydroamination of phenyl acetylene with aniline was carried out in toluene under reflux condition in N-2 atmosphere at 393 K. The reaction is highly regio-selective for only Markovnikoff's addition of an-tine to CC multiple bond and proceeded smoothly to completion. The reaction conditions were optimized to obtain complete conversion with respect to phenyl acetylene. Reaction data showed that the activity of the catalyst in hydroamination reaction is greater at higher reaction temperatures and nonpolar solvents and NZ pressure promotes the reaction drastically. (c) 2005 Elsevier B.V. All rights reserved.</p>10aalkyne10aAniline10aCatalyst10ahydroamination10aK-10 montmorillonite clay10aphenyl acetylene1 aJoseph, Trissa1 aShanbhag, G., V.1 aHalligudi, Shivappa, B.  uhttps://library.ncl.res.in/content/copperii-ion-exchanged-montmorillonite-catalyst-direct-addition-n-h-bond-cc-triple-bond-002717nas a2200301   4500008004100000022001400041245010700055210006900162260007300231300001200304490000800316520171400324653001202038653001802050653002302068653001002091653000702101653001302108653002002121653001802141653002302159100001802182700001602200700002802216700001802244700003002262856012302292       2005                        eng d  a1381-116900aInsight into the mechanism of selective mono-N-methylation of aniline on Cu1-xZnxFe2O4: a DRIFTS study0 aInsight into the mechanism of selective monoNmethylation of anil  aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcAPR  a169-1800 v2313 a<p>Mechanism of selective mono-N-methylation of aniline with methanol on Cu1-xZn2FeO4 catalysts was investigated in detail. The interaction of reactants (aniline. methanol and methanol: aniline) and possible products (N-methylaniline (NMA), N,N-dimethylaniline (DMA) and o-toluidine (OT)) on catalysts surface was studied by temperature-dependent in situ FTIR spectroscopy. Methanol adsorbs dissociatively over catalysts surface at 373 K as methoxy species and is oxidized to formate species at high temperature through dioxymethylene and/or formaldehyde as a surface intermediate species. On the other hand, adsorption of aniline:methanol mixtures shows that methanol oxidation was completely hindered in the presence of aniline. Aniline adsorbs on the Lewis acid sites at &lt;= 373 K with phenyl ring oriented in a perpendicular manner to the catalyst surfaced however, N-H bond scission occurs above 373 K. A comparison of adsorbed NMA and methanol: am line (3:1) mixture on Cu0.5Zn0.5Fe2O4 shows NMA forms from the reaction mixture at 473 K. However, maximum activity at 573 K in catalytic reaction studies suggests that desorption limits the methylation kinetics. FTIR study displays stable aniline and methyl species on ZnFe2O4 even at 573 K; however. no methyl species is detected on Cr0.95Zn0.05Fe2O4 at 473 K due to methanol reforming reaction and that limits the overall reaction and hence low catalytic activity. It is proposed that methanol is protonated on catalysts surface by the labile H+ due to N-H bond scission. Co-adsorption of acidity probes with aniline and methanol indicates that aniline methylation takes place at single acid-base site. (c) 2005 Elsevier B.V. All rights reserved.</p>10aAniline10aCu1-xZnxFe2O410adesorption limited10aDRIFT10aIR10aMethanol10aN-methylaniline10aN-methylation10areaction mechanism1 aVijayaraj, M.1 aMurugan, B.1 aUmbarkar, Shubhangi, B.1 aHegde, S., G.1 aGopinath, Chinnakonda, S.  uhttps://library.ncl.res.in/content/insight-mechanism-selective-mono-n-methylation-aniline-cu1-xznxfe2o4-drifts-study-001913nas a2200253   4500008004100000022001400041245013700055210006900192260007300261300001000334490000800344520099500352653001201347653002301359653001601382653000601398653001701404653002301421653001601444100002201460700001801482700002901500856013001529       2005                        eng d  a1381-116900aSelective synthesis of N,N-dimethyl aniline derivatives using dimethyl carbonate as a methylating agent and onium salt as a catalyst0 aSelective synthesis of NNdimethyl aniline derivatives using dime  aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcFEB  a49-560 v2263 a<p>N-Alkylation of anilines by dimethyl carbonate (DMC) catalyzed by onium salts has been demonstrated. The work presented here shows that a simple catalytic system consisting of onium salts in the presence of a small amount of water is extremely effective in enhancing the DMC mediated N-alkylation of anilines to dialkylated products. The effect of reaction conditions on the synthesis of N,N-dimethyl aniline (NNDMA) from aniline and DMC has been investigated. Under the optimized conditions highest yield of NNDMA obtained was 99.8%, which is the best reported for liquid phase N-alkylation of aniline using DMC. The role of water in enhancing the yield of NNDMA is explained and a reaction-networking scheme is constructed, which summarizes the chemistry behind liquid phase N-alkylation of anilines by DMC. The catalyst has been shown to recycle up to five times and at the end of fifth recycle almost 98% of NNDMA yields were obtained. (C) 2004 Elsevier B.V. All rights reserved.</p>10aAniline10aDimethyl carbonate10amethylation10aN10aN-alkylation10aN-dimethyl aniline10aonium salts1 aShivarkar, A., B.1 aGupte, S., P.1 aChaudhari, Raghunath, V.  uhttps://library.ncl.res.in/content/selective-synthesis-nn-dimethyl-aniline-derivatives-using-dimethyl-carbonate-methylating-002227nas a2200265   4500008004100000022001400041245014400055210006900199260009500268300001000363490000800373520126800381653001201649653001201661653002001673653001801693653001101711653001501722653002501737653000801762653000801770100002401778700003001802856012901832       2006                        eng d  a0021-951700aOn the ``Active spacer and stabilizer'' role of Zn in Cu1-xZnxFe2O4 in the selective mono-N-methylation of aniline: XPS and catalysis study0 aActive spacer and stabilizer role of Zn in Cu1xZnxFe2O4 in the s  a525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USAbACADEMIC PRESS INC ELSEVIER SCIENCEcJUL  a83-950 v2413 a<p>A systematic catalytic methylation study on ferrospinel materials led to the selective production of N-methylaniline (NMA) with Cu1-xZnxFe2O4. Aniline methylation was carried out on Cu1-xZnxFe2O4 with a feed composition of CH3OH:PhNH2:H2O = 3:1:1 at 513-633 K. NMA was formed selectively on all of the catalyst compositions, with trace amounts of secondary products under most of the conditions. Cu0.5Zn0.5Fe2O4 composition showed high catalytic activity and stability up to 100 h. Although the Cu2+ was responsible for methylation activity, Zn2+ enhanced the overall stability of the catalyst system. XPS investigations revealed that the degree of Cu2+ reduction decreased dramatically from x = 0.05/0.25 to 0.5/0.75 on spent catalysts. TPR studies indicated that the reducibility of Cu2+ decreased from fully reducible at 523 K with Cu-rich compositions to partially reducible at 573 K on x = 0.5. Stable activity observed on Cu0.5Zn0.5Fe2O4 can be attributed to the highly heterogeneous distribution of metal ions. This heterogeneous distribution indicates an important role of zinc, likely as an ``active spacer cum stabilizee' that hinders the reduction of active Cu2+ and contributes to prolonged activity. (c) 2006 Elsevier Inc. All rights reserved.</p>10aAniline10aFerrite10aN-methylaniline10aN-methylation10aspacer10astabilizer10asurface distribution10aTPR10aXPS1 aVijayaraj, Munusamy1 aGopinath, Chinnakonda, S.  uhttps://library.ncl.res.in/content/active-spacer-and-stabilizer-role-zn-cu1-xznxfe2o4-selective-mono-n-methylation-aniline-101277nas a2200241   4500008004100000022001400041245012000055210006900175260008900244300001200333490000700345520039200352653001200744653001700756653001300773653002400786653002200810100002100832700001500853700001900868700001600887856013200903       2006                        eng d  a0376-469900aNatural kaolinitic clay: a remarkable catalyst for highly regioselective chlorination of arenes with Cl-2 or SO2Cl20 aNatural kaolinitic clay a remarkable catalyst for highly regiose  aDR K S KRISHNAN MARG, NEW DELHI 110 012, INDIAbNATL INST SCIENCE COMMUNICATIONcAPR  a972-9750 v453 a<p>Natural kaolinitic clay containing transition metals such as Fe and Ti in its lattice has been found to exhibit unusual regioselectivity in the liquid-phase chlorination of arenes with either Cl-2 or SO2Cl2 as the chlorinating agent para-Chlorinated products are predominant for most of the substrates with an exceptional case of ortho-selectivity for the chlorination of aniline.</p>10aAniline10achlorination10achlorine10aortho-chloroaniline10asulfuryl chloride1 aJayachandran, B.1 aPhukan, P.1 aDaniel, Thomas1 aSudalai, A.  uhttps://library.ncl.res.in/content/natural-kaolinitic-clay-remarkable-catalyst-highly-regioselective-chlorination-arenes-cl-2-001737nas a2200217   4500008004100000022001400041245009700055210006900152260007300221300001200294490000700306520095500313653001501268653001201283653001901295653002401314653002001338100001801358700002201376856012101398       2009                        eng d  a0169-131700aSelective N-alkylation of aniline with methanol over a heteropolyacid on montmorillonite K100 aSelective Nalkylation of aniline with methanol over a heteropoly  aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcMAY  a255-2580 v443 a<p>N-methylaniline is an industrially important product in the manufacture of paper, textile dyes, drugs, perfumes and explosives. The vapour phase alkylation of aniline with methanol forming N-methylaniline is advantageous over liquid phase alkylation. In present study, vapour phase methylation of aniline over dodecatungestophosphoric acid supported on K10 montmorillonite was systematically studied and optimization of process parameters was carried out. The 20% m/m DTPA/K10 was found to be optimum with 79% aniline conversion and 99% N-methylaniline selectivity. The reaction required milder operating conditions than reported for commercial catalysts. We also studied the feasibility of 20% m/m DTPA/K10 as a catalyst for the alkylation of aniline with other alcohols like ethanol, n-propanol, iso-propanol and n-butanol. The activity of 20% m/m DTPA/K10 decreased with increasing carbon number. (C) 2009 Elsevier B.V. All rights reserved.</p>10aAlkylation10aAniline10aHeteropolyacid10amontmorillonite K1010aN-methylaniline1 aNehate, Manoj1 aBokade, Vijay, V.  uhttps://library.ncl.res.in/content/selective-n-alkylation-aniline-methanol-over-heteropolyacid-montmorillonite-k10-001711nas a2200253   4500008004100000022001400041245009700055210006900152260005700221300001200278490000800290520085800298653001201156653001501168653001301183653002001196653001101216100002201227700001801249700001801267700002701285700002201312856012301334       2009                        eng d  a1011-372X00aSynthesis of N-methylaniline by aniline alkylation with methanol over Sn-MFI molecular sieve0 aSynthesis of Nmethylaniline by aniline alkylation with methanol   a233 SPRING ST, NEW YORK, NY 10013 USAbSPRINGERcNOV  a175-1840 v1333 a<p>Sn-MFI molecular sieves (Tin silicalite-1) with SiO(2)/SnO(2) molar ratio of 50-150 were synthesized and characterized. Elemental analysis, XRD and DRUV-vis confirmed that prepared samples were of MFI zeolite structure and Sn was incorporated in MFI framework. Vapor phase methylation of aniline over Sn-MFI was systematically studied and optimizations of process parameters were carried out. Sn-MFI (SiO(2)/SnO(2) = 50) was found to be optimum catalyst with 55% aniline conversion and 60% N-methylaniline selectivity. At lower space velocity (higher contact time) of 1 h(-1), aniline conversion was found to be increased to 71% with reduction in N-methylaniline selectivity to 39% and increased in N,N-dimethylaniline selectivity to 58%. The reaction follows first order kinetics with respect to aniline having activation energy of 7.3 kcal/mol.</p>10aAniline10aLewis acid10aMethanol10aN-methylaniline10aSn-MFI1 aNiphadkar, P., S.1 aJoshi, P., N.1 aGurav, H., R.1 aDeshpande, Suvarna, S.1 aBokade, Vijay, V.  uhttps://library.ncl.res.in/content/synthesis-n-methylaniline-aniline-alkylation-methanol-over-sn-mfi-molecular-sieve-002289nas a2200241   4500008004100000022001400041245013400055210006900189260007300258300001200331490000800343520139200351653001401743653001201757653002801769653001301797653002001810100002201830700001801852700002701870700002201897856012801919       2011                        eng d  a0926-860X00aInfluence of Al3+ insertion in the stannosilicate MFI framework on the catalytic performance in vapor phase aniline N-methylation0 aInfluence of Al3 insertion in the stannosilicate MFI framework o  aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJUL  a182-1880 v4013 a<p>Silica-based Sn-MFI, Al-MFI and Al-Sn-MFI molecular sieves were synthesized by hydrothermal crystallization of gels having molar compositions SiO2:xSnO(2):yAl(2)O(3):0.23 (TPA)(2)O:35H(2)O, where x ranges from 1/0 to 1/200 and y from 1/0 to 1/400. Keeping molar Si/(Al + Sn) = 50, the amount of tin and aluminum in hydrogel was varied (Sn:Al molar ratios = 1:0, 1:0.33, 1:1, 1:3, 0:1) to investigate the synergy between Lewis and Bronsted acid sites in acid catalyzed aniline N-methylation reaction. Catalyst characterization was done by Powder X-ray diffraction, DRUV-vis spectroscopy, temperature programmed ammonia desorption (TPAD) and FTIR spectroscopy. An increase in the Al3+ insertion in Sn-MFI framework resulted in the increase in the stronger acid sites. Al-Sn-MFI showed higher aniline conversion than their monometallic counterparts. A sample having B/L ratio in between 0.67 and 0.91 was found to be optimum for maximizing the NMA yield, indicating the existence synergistic properties of Al-Sn-MFI. Upon process parameter optimization, the optimum sample M50 [Si/Al = 50.2, Si/Sn = 93.8, Si/(Al + Sn) = 43.2] showed the maximum aniline conversion (67%) and NMA selectivity (81%) at reaction temperature = 220 degrees C, weight hourly space velocity (WHSV) = 3 h(-1), molar ratio (aniline to methanol) = 1:8 and TOS = 4 h. (C) 2011 Elsevier B.V. All rights reserved.</p>10aAl-Sn-MFI10aAniline10aBronsted and Lewis acid10aMethanol10aN-methylaniline1 aNiphadkar, P., S.1 aJoshi, P., N.1 aDeshpande, Suvarna, S.1 aBokade, Vijay, V.  uhttps://library.ncl.res.in/content/influence-al3-insertion-stannosilicate-mfi-framework-catalytic-performance-vapor-phase-002040nas a2200277   4500008004100000022001400041245014700055210006900202260000900271300001400280490000700294520113500301653001201436653000801448653000901456653001301465653001201478653001201490100002601502700002501528700002401553700002201577700001901599700002001618856012401638       2023                        eng d  a0149-639500aLiquid-liquid equilibria of ternary mixtures containing Aniline plus Toluene plus water at elevated temperatures: measurements and correlation0 aLiquidliquid equilibria of ternary mixtures containing Aniline p  cNOV   a2718-27250 v583 a<p>
	Liquid-liquid equilibrium (LLE) data for the ternary system, Aniline + Toluene + Water, was measured at different temperatures of 298.15 K, 313.15 K and 323.15 K under atmospheric pressure with the help of High-Performance Liquid Chromatography (HPLC) analysis and Karl-Fischer technique. The efficiency of Toluene to extract Aniline from aqueous phase was then quantified in terms of the distribution coefficient and separation factor based on the tie line data. The system showed very good separation ability quantified in terms of high values of distribution factor (average around 7) and separation factors (as high as 1000). The experimental tie line data was verified by Hand and Othmer-Tobias equations. The LLE data was also correlated using NRTL and UNIQUAC models and both of them were able to represent the behavior of the system accurately when tested against experimental results. Toluene has been demonstrated to be very efficient to extract Aniline from reaction mixture, which is typically a by-product in hydrogenation of nitrobenzene, a process commercially used to produce p-Aminophenol in industry.</p>
10aAniline10aLLE10aNRTL10aTie line10aToluene10aUNIQUAC1 aGaikwad, Shashank, G.1 aPathak, Abhishek, A.1 aMote, Dhananjay, R.1 aGogate, Parag, R.1 aSingh, Shivani1 aModhera, Bharat  uhttps://library.ncl.res.in/content/liquid-liquid-equilibria-ternary-mixtures-containing-aniline-plus-toluene-plus-water