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Jackson and Spence 243been related to enhancing surface hydrogen transfer due to changes in retainedspecies (5).The alkene selectivity as a function of conversion is shown in Figure 2.10080% Selectivity60402000 20 40 60 80 100% Conversion1PP TCN 3PPN 3PPA TCAFigure 2. Plot of conversion Vs selectivityThe average cis:trans ratio for methylstyrene was determined and is reported inTable 2.Table 2. Average cis:trans ratio of alkene intermediate in 1PP hydrogenation.1PP TCA TCN 3PPN 3PPA519 1164 1031 19 905It is clear from Figure 2 that the modifiers have an effect on the selectivity to thealkene. TCN and TCA modified systems maintain alkene selectivity at ≥ 90 % overthe full range of 1PP conversion. 3PPA modified system shows an enhancedselectivity but as conversion increases to 100 % there is a slight drop off. Thesethree modified systems all show higher alkene selectivity than the unmodified 1PP,which has a declining selectivity with conversion, but lies mainly between 80 – 60%. The TCA, TCN, 3PPA modifiers also affect the cis:trans ratio of themethylstyrene. Very high cis:trans ratios are observed in these systems. Theseresults show that the TCA, TCN, and 3PPA modifiers do inhibit re-adsorption of the
244 1-Phenyl-1-Propynealkene. When there is little or no re-adsorption, the production of phenylpropane isinhibited. At 55 % conversion, 1PP hydrogenation modified with TCA producesonly 13 % of the amount of phenyl-propane that is produced in the absence of themodifier. At 100 % conversion of 1PP a similar reduction is seen when TCN is themodifier. This inhibition of alkene re-adsorption is also observable in the cis:transratio of methylstyrene. The high cis:trans values confirm that cis-β-methylstyrene isthe primary product with only around 0.1 % of the alkene produced being trans-βmethyl-styrene.When re-adsorption and isomerisation occur the cis:trans valuedrops to 19, reflecting the thermodynamic drive to produce the trans isomer.Therefore the unsaturated aldehyde, the unsaturated nitrile, and the saturatedamine all bond more strongly than methylstyrene to the palladium surface. Thesaturated amine has adsorption energetics that are close to those of methylstyreneshowing only a limited effect. The saturated nitrile however enhances not just thealkyne hydrogenation but also the alkene hydrogenation. This suggests that thesaturated nitrile affects the rate determining hydrogen transfer aspect of thehydrogenation. Rate enhancement effects have been previously observed incompetitive reaction systems containing alkynes and alkenes (4, 5) and a similarconclusion drawn. The exact mode of operation is however unclear and requiresfurther investigation.Experimental SectionThe catalyst used throughout this study was a 1% w/w palladium on aluminasupplied by Johnson Matthey. The support consisted of θ-alumina trilobes (S.A.~100 m 2 g -1 ) and the catalyst was sized to 99 %) were used without further purification.No significant impurities were detected by GC. The gases (BOC, >99.99 %) wereused as received.The reaction was carried out in a 0.5 L Buchi stirred autoclave equipped with anoil jacket and a hydrogen-on-demand delivery system. 0.05 g of catalyst was addedto 278 mL of degassed solvent, propan-2-ol. Reduction of the catalyst wasperformed in situ by sparging the solution with H 2 (300 cm 3 min -1 ) for 30 minutes at343 K at a stirring speed of 300 rpm. After reduction, the autoclave was adjusted to313 K under a nitrogen atmosphere and 1 mL of modifier was added in 10 mL ofdegassed propan-2-ol. The system was pressurized to 3 bar hydrogen and the stirrerset to 1000 rpm. After 1 h, 1 mL of 1-phenyl-1-propyne was added to the reactor in10 mL of degassed solvent. Samples were taken at defined time intervals andanalyzed by GC. Specific reactions were repeated at different stirrer speeds andequivalent rates and selectivities were observed indicating and absence of masstransfer within the system.
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Catalysis ofOrganic Reactions
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14. Catalyst Manufacture: Laborator
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62. Catalysis of Organic Reactions,
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108. Metal Oxides: Chemistry and Ap
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CRC PressTaylor & Francis Group6000
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xiii14. The Transformation of Light
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xviien Catalisis y Petroquimica (UN
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xix56. Transition Metal Removal fro
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xxiiiChronology of Organic Reaction
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To Zsuzsanna and Tim
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Jones et al. 31. On the Use of Immo
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Jones et al. 5three-phase tests in
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Jones et al. 7In the HKR of rac-epi
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Jones et al. 9term performance char
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Jones et al. 115. A. S. Gruber, D.
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Moses et al. 132. Supported Re Cata
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Moses et al. 15perrhenate, followed
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Moses et al. 17SnCOSnMe 4≡SiOReO
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Moses et al. 19(AlOSi) of the cube.
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Moses et al. 212.510 3 k obs / s -1
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Wang et al. 233. Catalytic Hydrogen
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Wang et al. 25The rate expressions
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Wang et al. 27Schiff’s base forma
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Wang et al. 29AcknowledgementsWe gr
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32Halophosphite LigandsIn 1970, Pru
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34Halophosphite LigandsThe ligands,
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36Halophosphite LigandsTable 2 Temp
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38Halophosphite Ligands3. P. W. N.
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40Monolithic Bioreactorstrength for
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42Monolithic BioreactorMenten equat
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Gőbölös et al. 456. Highly Selec
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Gőbölös et al. 47was practically
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Gőbölös et al. 49noteworthy that
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Gőbölös et al. 51Figure 2 NMR sp
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Gőbölös et al. 53internal TMS in
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56Hydrotalcite-like Catalysts[A n-
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58Hydrotalcite-like Catalystssample
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Mantilla, Tzompantzi, Torres and G
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68Synthesis of MIBKwe examined the
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70Synthesis of MIBK1412Conversion (
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72Synthesis of MIBK4,4’-dimethyl
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74Synthesis of MIBKobtained for MIB
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Ardizzi et al. 7710. The Control of
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Ardizzi et al. 79type acidity at th
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Ardizzi et al. 81procedure describe
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84Phenol Benzoylationconsecutive Fr
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86Phenol BenzoylationThis does not
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II. Symposium on Catalytic Oxidatio
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92Oxidation with Microchannel Immob
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100 Propylene Partial OxidationThe
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102 Propylene Partial OxidationSiO
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104 Propylene Partial Oxidation0.01
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106 Propylene Partial Oxidation0.02
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108 Propylene Partial OxidationRefe
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110Oxidation of n-Pentanemethacryli
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112Oxidation of n-PentaneFReqox1ox2
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114Oxidation of n-Pentanethe presen
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116Oxidation of n-PentaneIn the mec
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118Oxidation of n-PentaneReferences
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120TEMPO Oxidation of Alcoholsthe u
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122TEMPO Oxidation of AlcoholsThe r
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124TEMPO Oxidation of Alcoholsany d
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126TEMPO Oxidation of Alcoholsconce
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128TEMPO Oxidation of AlcoholsMNT :
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130TEMPO Oxidation of Alcoholsuptak
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132Aminoalcohols to Aminocarboxylic
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142Bromine-Free TEMPO-Based Catalys
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148CO OxidationP25 TiO 2 , respecti
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150CO Oxidation0.02(a)21802110(b)21
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152CO Oxidationcarboxylate species
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Yamauchi 15519. 2006 Murray Raney A
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Yamauchi 157transformation is schem
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Yamauchi 159The X-ray diffraction p
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Yamauchi 161was -0.0009, -0.0032 an
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Yamauchi 163shown in Fig. 12. It wa
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168Nitrobenzene Hydrogenationfurthe
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170Nitrobenzene Hydrogenationhydrog
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172Nitrobenzene HydrogenationThe co
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174Nitrobenzene HydrogenationHence
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176Nitrobenzene Hydrogenation10. G.
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178 Hydrogenation of Dehydrolinaloo
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188Modeling Mass Transfer Hydrogena
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190Modeling Mass Transfer Hydrogena
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Page 260 and 261: Ostgard et al. 233In conclusion, th
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Page 294 and 295: Rothenberg et al. 267Table 1. Parti
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294Chiral Ferrocene Ligandsnew Twin
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296Chiral Ferrocene LigandsTable 1.
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298Chiral Ferrocene Ligandsprevents
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300Chiral Ferrocene LigandsConclusi
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302Chiral Ferrocene Ligandsextracte
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304 Catalyst Library DesignIn gas p
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306 Catalyst Library Designd−(b 0
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308 Catalyst Library DesignBasic Pr
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310 Catalyst Library DesignD in com
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312 Catalyst Library DesignCatalyst
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314 Catalyst Library Design27. S. H
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316 Dendrimer TemplatesWe are devel
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318 Dendrimer TemplatesThe differen
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320 Dendrimer TemplatesWe encounter
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322 Dendrimer TemplatesThe 100 cm -
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328Rearrangement of 3,4-Epoxy-1-But
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3382,5-Dimethyl-2,4-Hexadieneharves
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348Heteropoly AcidsSOOO O+ +OS1 2 3
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350Heteropoly AcidsTable 3. Acylati
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352Heteropoly AcidsSiO 2 is the bes
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Diez, Di Cosimo and Apesteguia 3554
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378 Polyurethane from Natural OilMe
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380 Polyurethane from Natural Oilco
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382 Polyurethane from Natural Oilfr
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384 Polyurethane from Natural OilTh
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386 Carbonylation of Chloropinacolo
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396 Recycling Homogeneous Catalysts
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406“Green” Catalysts for Biodie
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416 Production of BiodieselTable 1.
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418 Production of Biodieselto a mas
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420 Production of BiodieselEthyl st
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422 Production of Biodiesel10080Sel
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424 Production of Biodieselproduct
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Marincean et al. 431neutralize all
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Marincean et al. 433suggesting that
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Kocal 43748. Developing Sustainable
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Kocal 439description of the four st
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Kocal 441metallurgy in parts of the
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Kocal 443that capital investment co
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448Propylene Oxidation to POSupercr
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450Propylene Oxidation to POTable 1
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452Propylene Oxidation to PO
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Riermeier et al. 45550. catASium ®
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Riermeier et al. 457It is interesti
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Riermeier et al. 459Reaction of the
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464 Chiral 2-Amino-1-Phenylethanolp
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466 Chiral 2-Amino-1-PhenylethanolI
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468 Chiral 2-Amino-1-Phenylethanola
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470 t-Butanol DehydrationResults an
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472 t-Butanol Dehydrationcomprises
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Pohlmann et al 47553. Leaching Resi
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Pohlmann et al 477this study. In th
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Pohlmann et al 479Experimental Sect
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482 Reductive AlkylationSince the p
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484 Reductive AlkylationTable 2. Re
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Wolf, Seebald and Tacke 489100Norma
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Woods et al. 49356. Transition Meta
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Woods et al. 495Effect of oxidation
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502 Electroreductive Catalytic Ullm
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504 Electroreductive Catalytic Ullm
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Catalysis of Organic Reactions 507A
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Catalysis of Organic Reactions 509K
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Catalysis of Organic Reactions 511T
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514 Keyword Indexcarboncarbon dioxi
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516 Keyword Indexethanolamine 16 13
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518 Keyword IndexNi, activated 25 2
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520 Keyword Indexsuccinimido ketone
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