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Woods et al. 49356. Transition Metal Removal fromOrganic Media by Deloxan ® Metal ScavengersJaime B. Woods 1 , Robin Spears 1 , Jürgen Krauter 2 , Tim McCarthy 3 , MichealMurphy 3 , Lee Hord 4 , Peter Doorley 4 , Baoshu Chen 11Degussa Corporation, Business Line Catalysts, 5150 Gilbertsville Highway,Calvert City, KY 42029, USA2Degussa AG, Business Line Catalysts, Rodenbacher Chaussee 4, D-63457,Hanau, Germany3Degussa Corporation, Business Line Catalysts, 379 Interpace Parkway,Parsippany, NJ, 07054, USA4Mobile Process Technology, 2070 Airways Boulevard, Memphis,TN 38114, USAjaime.woods@degussa.comAbstractCatalysis is a valuable and indispensable tool in organic synthesis. Transitionmetals, most preferably precious metals, are often used. However, potential residualmetal contamination from these heterogeneously or homogeneously catalyzedreactions may be detrimental to product quality or, as in the case of activepharmaceutical ingredients (API’s), the metal concentration in the final product maybe regulated. Degussa’s Deloxan ® Metal Scavengers recover valuable preciousmetals from reaction mixtures and reduce the metal concentration in processsolutions to an acceptable level (
494 Transition Metal Removalmetal residue permitted to remain in pharmaceutical products is strictly regulated andfor Pd and other platinoid metals this level should be below 5 ppm.[2]Several methods of metal removal from process solutions exist. Some of theseapproaches include crystallization, distillation and extraction. However, thesemethods can be very time-consuming and often result in loss of some valuableproduct. To overcome these shortcomings, Degussa has developed Deloxan ® MetalScavengers as an attractive option to solve problems associated with transition metalcontamination of process solutions.[3, 4, 5] Two resins are commercially available.Deloxan ® THP II (1) is a thiourea functionalized, macroporous, organofunctionalpolysiloxane while Deloxan ® MP (2) is mercapto functionalized.These Deloxan ® beads have an inert siloxane matrix which is advantageous overother adsorbents such as activated carbon or organic polymer-based resins and fibersbecause (1) valuable API product is not adsorbed and lost as is the case whenactivated carbons are used and (2) they are chemically resistant to most solvents andstable over a wide pH range (0–12).OOOOSiOSiOCH 2 CH 2CH 2 CH 2CH 2CH 2NHNHCSOOSiOSiOCH 2 CH 2CH 2 CH 2CH 2CH 2SHSH1 2In addition to these, Deloxan ® THP II and MP possess many othercharacteristics that are essential for good metal scavenging. First, they have good toexcellent scavenging properties for most transition metals. They are structurallystable showing no shrinking or swelling and compatible with all solvents. These arehighly attrition resistant and thermally stable. Deloxan ® Metal Scavengers have awell-defined pore structure and due to the bead size (0.4–1.4 mm) and shape theycan be applied in either fixed bed or batch mode. They can be refined allowing forrecovery of precious metals. Importantly, Deloxan ® THP II and MP arecommercially available in large quantities.Results and DiscussionDue to the particle size of Deloxan ® THP II and MP, these resins can be used ineither batch or fixed bed mode to scavenge transition metals from contaminatedprocess solutions. In this work both modes of operation were investigated. Inaddition to mode of use, many other variables can influence the effectiveness of ametal scavenger. Oxidation state of the metal, solvent characteristics (polar ornonpolar) and nature of the metal complex (ligands) are just a few of these variablesand these were chosen for investigation in this body of work.
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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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Yamauchi 165These fine particles we
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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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198 Fructose HydrogenationHOHCCH 2O
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200 Fructose HydrogenationTable 1.
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202 Fructose Hydrogenationmmol form
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204 Fructose Hydrogenationthe subst
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206 Fructose Hydrogenationcleave th
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208 Fructose Hydrogenationfulfills
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210 Fructose Hydrogenationis not th
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Disselkamp et al. 21324. Cavitating
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Disselkamp et al. 215column. In a p
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Disselkamp et al. 217selectivity es
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Disselkamp et al. 219hydrogenated (
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Disselkamp et al. 221A somewhat mor
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Disselkamp et al. 223Scheme 4.cis-2
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Disselkamp et al. 225conventional c
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Ostgard et al. 22725. The Treatment
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Ostgard et al. 229Table 1. The reac
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Ostgard et al. 231metal atoms. Thes
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Ostgard et al. 233In conclusion, th
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Kuusisto, Mikkola and Salmi 23526.
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Kuusisto, Mikkola and Salmi 237100A
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Kuusisto, Mikkola and Salmi 2399. B
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242 1-Phenyl-1-Propyneof cis-β-met
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244 1-Phenyl-1-Propynealkene. When
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Musolino, Apa, Donato and Pietropao
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Gőbölös and Margitfalvi 25329. R
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Gőbölös and Margitfalvi 255maxim
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Gőbölös and Margitfalvi 257Y=421
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Rothenberg et al. 26130. How to Fin
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Rothenberg et al. 263By dividing th
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Rothenberg et al. 265pre-define the
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Rothenberg et al. 267Table 1. Parti
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Rothenberg et al. 269Experimental S
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Angueira and White 27131. Novel Chl
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Angueira and White 273optimizedgeom
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Angueira and White 275F igure 4 - c
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Angueira and White 277Table 1. 27 A
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Angueira and White 279obtained from
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Robitaille, Clément, Chapuzet and
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Cao, White, Wang and Frye 28933. Se
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Cao, White, Wang and Frye 291Experi
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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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3422,5-Dimethyl-2,4-Hexadiene10086Y
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3462,5-Dimethyl-2,4-Hexadiene8. www
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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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Diez, Di Cosimo and Apesteguia 357T
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Diez, Di Cosimo and Apesteguia 359A
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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. 42747. Glycerol Hy
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Marincean et al. 429Experimental Se
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Marincean et al. 431neutralize all
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Marincean et al. 433suggesting that
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Marincean et al. 435increasing from
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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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Page 475 and 476: 448Propylene Oxidation to POSupercr
Page 477 and 478: 450Propylene Oxidation to POTable 1
Page 479 and 480: 452Propylene Oxidation to PO
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Page 484 and 485: Riermeier et al. 457It is interesti
Page 486 and 487: Riermeier et al. 459Reaction of the
Page 488: Riermeier et al. 461References1. I.
Page 491 and 492: 464 Chiral 2-Amino-1-Phenylethanolp
Page 493 and 494: 466 Chiral 2-Amino-1-PhenylethanolI
Page 495 and 496: 468 Chiral 2-Amino-1-Phenylethanola
Page 497 and 498: 470 t-Butanol DehydrationResults an
Page 499 and 500: 472 t-Butanol Dehydrationcomprises
Page 502 and 503: Pohlmann et al 47553. Leaching Resi
Page 504 and 505: Pohlmann et al 477this study. In th
Page 506: Pohlmann et al 479Experimental Sect
Page 509 and 510: 482 Reductive AlkylationSince the p
Page 511 and 512: 484 Reductive AlkylationTable 2. Re
Page 514 and 515: Wolf, Seebald and Tacke 48755. Acce
Page 516 and 517: Wolf, Seebald and Tacke 489100Norma
Page 518 and 519: Wolf, Seebald and Tacke 4911,88Figu
Page 522 and 523: Woods et al. 495Effect of oxidation
Page 524 and 525: Woods et al. 497
Page 526: Woods et al. 499removed the samples
Page 529 and 530: 502 Electroreductive Catalytic Ullm
Page 531 and 532: 504 Electroreductive Catalytic Ullm
Page 534 and 535: Catalysis of Organic Reactions 507A
Page 536 and 537: Catalysis of Organic Reactions 509K
Page 538: Catalysis of Organic Reactions 511T
Page 541 and 542: 514 Keyword Indexcarboncarbon dioxi
Page 543 and 544: 516 Keyword Indexethanolamine 16 13
Page 545 and 546: 518 Keyword IndexNi, activated 25 2
Page 547: 520 Keyword Indexsuccinimido ketone
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