Hydroformylation
Detlef Selent,a Klaus-Diether Wiese,b and Armin B rner3 aLeibniz-Institut f r Organische Katalyse, Buchbinderstr. 5-6, D-18055 bOxeno C-4 Chemie, Paul-Baumann-Str. 1, D-45772Marl Germany Bidentate phosphorus ligands bearing an O-acyl phosphite moiety show superior modifying properties to the rhodium catalyst used in the hydroformylation of internal olefins. Results obtained for the hydroformylation of internal octenes and 2-pentene, respectively, are presented. The new ligands do markedly...
Conclusions Xes
The RPT of Pt Al2O3 catalysts improves the hydrogenation TOF and ee while sintering the Pt crystallites. The degree of TOF and ee enhancement induced by RPT increases with higher levels of reducible residues due to the poor performance of the initial catalyst. Pt sintering and potential residue retention also increase if higher reducible residue contents are present. Such catalysts tend to perform worse, even after RPT, than those with lower amounts of reducible residues. A cleaner catalyst...
Rubber Catalyzed by [IrCODpyPCyPF
Jianzhong Hu, Neil T. McManus, Garry L. Rempel Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 The application of Ir COD PCy3 py PF6, COD 1,4 cyclooctadiene, PCy3 tricyclohexylphosphine, py pyridine Crabtree's catalyst 1 for the hydrogenation of nitrile butadiene rubber NBR has been investigated for the first time. The catalyst was efficient for selective hydrogenation of olefinic groups in NBR. A preliminary kinetic study was used to explore the...
Aromatics
Marta Catellani, Elena Motti, Sara Deledda, Fiorenza Faccini Dipartimento di Chimica Organica e Industriale dell'Universita, Parco Area delle Scienze, 17 A, 43100 Parma, Italy Alkylaromatic palladacycles, formed in situ by reaction of palladium acetate with a strained and rigid cycloolefin such as norbornene and an ortho-substituted aryl iodide, allow the selective arylation of the aromatic ring by a second molecule of aryl iodide with subsequent norbornene expulsion. Coupling the resulting...
Nickel Catalyst
Gregory J. Ward and Bryan C. Blanchard Solutia, Inc., P.O. Box 97, Gonzalez, FL 32560-0097 A process for the production of 3-dimethylaminopropylamine DMAPA in high gt 99 purity from N,N-dimethylaminopropionitrile DMAPN utilizing a low pressure slurry hydrogenation process is described. The basic process comprises contacting the nitrile with hydrogen at low pressure in the presence of a sponge nickel catalyst under conditions sufficient to effect the conversion of the nitrile to the primary...
Abstract 1
The carbobenzyloxy group Cbz or Z is a very useful protecting group in organic synthesis, in particular for the synthesis of proteins and peptides, which are used as drug intermediates. The Cbz group can be easily removed via catalytic hydrogenation. Typically, Pd supported on activated carbon powder is the catalyst of choice for such reaction 1 . In this work, we report a more active 5 Pd on activated carbon catalyst for the deprotection of Cbz-phenylalanine. This new Degussa Cbz catalyst is...
Design and Parallel Reactors
Venu Arunajatesan, ShaRee L. McIntosh, Marisa Cruz, Roman F. Degussa Corporation, 5150 Gilbertsville Hwy, Calvert City, KY, 42029 In this paper we report a method for the rapid optimization of process conditions for a model reaction selective hydrogenation of phenol to cyclohexanone over Pd C in liquid phase , which in general could be applied to any reaction. Our goal is to optimize the process conditions that would maximize the yield of cyclohexanone within the reaction constraints. The...
Nylon Recycle Process
Alan M. Allgeier, Theodore A. Koch, and Sourav K. Sengupta INVISTA Nylon Intermediates Experimental Station, Wilmington, DE19880-0302 A process for the hydrogenation of adiponitrile and 6-aminocapronitrile to hexamethylenediamine in streams of depolymerized Nylon-6,6 or a blend of Nylon-6 and Nylon-6,6 has been described. Semi-batch and continuous hydrogenation reactions of depolymerized ammonolysis products were performed to study the efficacy of Raney Ni 2400 and Raney Co 2724 catalysts. The...
Results and Discussion
Figure 1 shows the infrared spectra of the reactant and product mixture taken as a function of time over PdCl2 PPh3 2. The characteristic bands of carbamate at 1713-1731 cm-1 and 1607-1620 cm-1 increased with the reaction time. The former is due to the C O stretching vibration the latter is due to the N-H bending vibration in carbamate. The 13C NMR spectrum of the product sample gave a carbamate's C O peak at 154.5 ppm. Both IR and NMR results confirmed the formation of ethyl-N-phenyl carbamate...
Rop Cp
Figure 5 Simplified reaction scheme. It is helpful to look at the comparison of ROP and CP at the same conversion levels to explain this phenomenon Figure 6 . While the concentrations of Iso and ROP are, at comparable conversion, the same for proton- and Pt-form of zeolites, the concentrations of CP are substantially lower over Pt-zeolites. Heavy products HP concentrations are lower with Pt-zeolites as well, even though the difference is not as marked as in the case of CP. The different...
Solid Acid Catalysed Esterification of Amino Acids and Other BioBased Acids
N. S. Asthana, Z. Zhang, and Dennis J. Miller 2527 Engineering Building, Department of Chemical Engineering amp Material Science, Michigan State University, East Lansing, MI 48824 Esters represent an important class of chemical compounds with applications as solvents, plasticizers, flavors and fragrances, pesticides, medicinals, surfactants, chemical intermediates, and monomers for resins. Recently, esters of amino acids have attracted attention regarding their use as biobased surfactants with...
Enhancement of Regioselectivity in the Gasphase Methylation of mCresol with
F. Cavani,1 L. Dal Pozzo,1 C. Felloni,1 L. Maselli D. Scagliarini,1 'Dipartimento di Chimica Industriale e dei Materiali, Viale Risorgimento 4, 40136 Bologna, Italy. INSTM, research unit of Bologna. 2EniTecnologie SpA, via Maritano 26, 20097 S. Donato MI, Italy Mg Me Me Al, Fe mixed oxides prepared from hydrotalcite precursors were compared in the gas-phase m-cresol methylation in order to find out a relationship between catalytic activity and physico-chemical properties. It was found that the...
Organic Synthesis
Jianping J. P. Chen and Charles R. Penquite Engelhard Corporation, 23800 Mercantile Road, Beachwood, OH 44122 This paper discusses typical properties of powdered precious metal catalysts related to catalytic performance in several organic syntheses. Some new developments and trends in precious metal catalysts, such as new generations of palladium DeLink , platinum and rhodium heterogeneous catalysts including immobilized homogeneous catalysts LiganNetTM for hydrogenation in organic synthesis...
The Aldol Condensation of Acetone Over a CsOHSiO Solid Base Catalyst
Arran S. Canning, S. David Jackson, Eilidh McLeod, and Elaine M. Vass Department of Chemistry, The University, Glasgow G12 8QQ, Scotland Abstract The solid base catalysed aldol condensation of acetone was performed over a CsOH SiO2 catalyst using a H2 carrier gas. The products observed were diacetone alcohol, mesityl oxide, phorone, iso-phorone and the hydrogenated product, methyl isobutyl ketone. Deuterium tracer experiments were performed to gain an insight into the reaction mechanism. A...
Results and Discussion Qat
The deprotection of the Cbz protected amino acid proceeds via a two step mechanism Figure 1 . The first step comprises the catalytic hydrogenolysis of the benzyloxy group of the Cbz-protected amino acid 1 . Toluene 3 is formed from the O-benzyl group as well as an unstable carbamic acid intermediate 2 . This intermediate decomposes to form the unprotected amino acid 4 and carbon dioxide 5 . Figure 1 Reaction scheme for the hydrogenolysis of a Cbz-protected amino acid. In our investigations, a...
Clean Diesel Fuel Production
David Kubicka,3 Narendra Kumar,a Paivi Maki-Arvela,3 Marja Tiitta,b Tapio Salmi,a and Dmitry Yu. Murzina aLaboratory of Industrial Chemistry, Process Chemistry Centre, Abo Akademi University, FIN-20500 Abo Turku, Finland bFortum Oil and Gas Oy, POB 310, FIN-06101 Porvoo, Finland The activity of H-Beta-25, H-Beta-75, H-Y-12, and of their Pt-impregnated counterparts has been investigated in the ring opening of decalin at 523 K in the presence of hydrogen. Ring opening was found to take place with...
the Reductive Carbonylation of Nitrobenzene over Pdbased Catalysts
Department of Chemical Engineering, The University of Akron, Akron OH Pd Al2O3-FeCl3, and Ce-Pd A Os-FeCls catalysts exhibit activity for the synthesis of ethylphenylcarbamate from the reductive carbonylation of nitrobenzene with ethanol at 453 K and 2.07 - 2.93 MPa. The advantage of the use of Al2O3-supported Pd catalyst is the easy of catalyst recovery form the reactants product mixture. Isocyanates are important chemical feedstock for the manufacture of fertilizers, pesticides, and various...
Isolated Organometallic Catalysts on Silica Supports Towards SingleSite Solid
Michael W. McKittrick, Shara D. McClendon, and School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA 30332 A well-defined amine functionalized silica surface displaying evidence of isolated amine sites is prepared using a molecular patterning technique. These aminosilicas serve as a support for immobilized organometallic catalysts, specifically constrained geometry catalysts for olefin polymerizations. The patterned catalysts show an activity of 27-32 kg...
Biaryl Synthesis
A. S. Kotnis, K. Zhu, B. L. Lotz, K. J. Natalie, J. H. Simpson, D. Kacusr, D. Thurston, J. S. Prasad, S. Mathew, and A. K. Singh Process Research and Development, Bristol-Myers Squibb Pharmaceuticals, The focus of this paper is on the preparation of biaryl moieties which are commonly present in a wide variety of pharmaceutically active compounds. Two different and practical approaches to synthesize the biaryl substructure will be discussed. Nature has an abundance of biologically interesting...
One Pot Transformation of Geraniol into Citronellol and Menthol over CuAlO
Nicoletta Ravasio,a Achille Fusi,b Rinaldo Psaro,a and Federica Zaccheriac CNR-ISTM, via Golgi 19,1-20133 Milano, Italy bDip. Chimica Inorganica, Metallorganica e Analitica, Universita di Milano, Via Venezian 21, I-20133 Milano cConsorzio INSTM, via B. Varchi 59, I-50132 Firenze, Italy Geraniol can be converted into citronellol and menthol over Cu Al2O3 under catalytic hydrogenation conditions owing to chemoselective hydrogenation and a three-functional process taking place on the catalyst...
Production of Ethyl Acetate
Flora T.T. Ng, Te Mure, Ming Jiang, Manzoor Sultan, Jin-hai Xie, and Pierre Gayraud Department of Chemical Engineering, University of Waterloo, Waterloo, Warren J. Smith, Matthew Hague, Robert Watt, and Steve Hodge BP Chemicals, Hull Research and Technology Center, Saltend, Hull, East Yorkshire, HU12 8DS, United Kingdom BP Chemicals is the world's largest producer of ethyl acetate. A common route for the production of ethyl acetate is via the esterification of ethanol with acetic acid. In 1997...