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Tanielyan et al. 129ConclusionsIt has been shown that the aerobic oxidation of alcohols takes place only when allthree components of the catalyst are present; AA TEMPO, Mg(NO 3 ) 2 , NBS (23).The reaction can be run under mild conditions: temperature 310-330K; oxygenpressure of 0.1-0.5Mpa; alcohol concentration of 5.4M in HOAc; ratio of substrate :AA TEMPO:Mg(NO 3 ) 2 :NBS = 133:1:1:1.19. Non-activated primary alcohols arequantitatively converted to the corresponding aldehydes at high selectivity. The onlyby-product observed in some instances is the corresponding carboxylic acid. Somesecondary alcohols were also oxidized with high selectivity to the correspondingketones but at lower conversions. Both benzyl alcohol and the sec-phenylethanolwere smoothly converted to their respective aldehyde or ketone oxidation products.Experimental SectionA. Experimental Setup. The oxidation reactions were performed using an in-housemade Multi Autoclave Glass Volumetric system (24). All reactions were carried outin Ace Glass reaction flasks with Teflon heads, equipped with Swagelock basedinjection and thermocouple ports. Digital stirrers and Fisher cross stir bars were usedfor providing an efficient and controlled stirring. The Multi Autoclave reactor systemallows conducting five simultaneous oxidations with five independent variables. Theonly common parameter for all five reactions is the reaction temperature. The reactorsystem permits the recording of the oxygen uptake with the time, thus allowingprecise monitoring the progress of the oxidation. The system was described in detailin our earlier work (24).B. Oxidation procedure for the small-scale experiments. The required amounts ofhexan-1-ol, AA-TEMPO, Mg(NO3)2, NBS and HOAc were loaded in the reactorand the flask was connected to the volumetric manifold. The flask was flushed threetimes with oxygen and immersed in the thermostated water bath held at the reactiontemperature for two minutes to equilibrate the system. The oxygen was admitted tothe reaction pressure and the continuous monitoring of the oxygen uptake initiatedand recorded against the time. After the reaction was completed the productcomposition was analyzed by GC using dioxane as an internal standard.C. Large-scale oxidation protocol. The large-scale oxidations reactions were carriedout in a 300mL Parr autoclave equipped with an injection port, a thermocouple port,a septa sealed addition port and port connected to the volumetric measurement andgas supply module. The module consists of a forward pressure regulator and acalibrated ballast reservoir. The pressure in the reactor and in the ballast reservoir ismonitored constantly and the pressure drop in the ballast reservoir is constantlyconverted into moles of oxygen uptake recorded vs. the time.In a typical oxidation reaction, the autoclave was charged with hexan-1-ol (100mL,800 mmol), HOAc (50 mL, 0.87mol), AA-TEMPO (1.28g, 6.0 mmol, 0.75 mol%),Mg(NO 3 ) 2 .6H 2 O (1.54g, 6mmol) and NBS (1.21g, 6.8mmol). The system waspurged three times with nitrogen, the nitrogen pressure increased to 150 psi and theautoclave heated to the desired temperature. When the target temperature wasreached, oxygen was admitted at 200 psi and the computer monitoring of the oxygen
130TEMPO Oxidation of Alcoholsuptake started. After the consumption of 390 mmol of oxygen, which under theseconditions was completed in 180 min, the autoclave was cooled to ambienttemperature, the pressure released and a sample taken for GC analysis.AcknowledgementsThis work was supported by Degussa Building Blocks.References1. S. Kirk-Othmer, Encyclopedia of Chemical Technology, 4 th ed., Wiley –Interscience, New York, Vol. 2, p. 481. 19922. M. Hudlicky, Oxidations in Organic Chemistry, ACS Monograph No. 186,American Chemical Society, Washington DC ,1990.3. R.A. Sheldon, J.K. Kochi, Metal-Catalysed Oxidations of OrganicCompounds; Academic Press, New York, 1981.4. J.R. Holum, J.Org.Chem., 26, 4814, (1961).5. D.G. Lee, U.A. Spitzer, J. Org. Chem., 35, 3589, (1970)6. R.J. Highet,; W.C. Wildman, J. Am. Chem. Soc., 78, 6682, (1958)7. S.-I. Murahashi, T. J. Naota, Synth. Org. Chem. Jpn., 46, 930, (1988).8. P. Anelli, C. Biffi, F. Montanari, and S. Quici, J. Org. Chem., 52, 2559, (1987)9. P. Anelli, S. Banfi, F. Montanari and S. Quici, J. Org. Chem., 54, 2970, (1989)10. A. E. J. de Nooy, A. C. Besemer, H. van Bekkum, Synthesis, 1153, (1996)11. P. L. Bragd, H. van Bekkum and A. C. Besemer, Topics in Catalysis, 27, 49,(2004)12. R. A. Sheldon, I. W. C. E. Arends, G. Brink and A. Dijksman, Acc. Chem. Res.,35, 774, (2002)13. S.K. Tanielyan, R.L. Augustine, I. Prakash, K.E. Furlong, R.C.Scherm, H.E.Jackson, PCT Int. Appl. WO 2004067484 (2004); I. Prakash, S.K. Tanielyan,R.L. Augustine, K.E. Furlong, R.C.Scherm, H.E. Jackson, US Pat. # 6,825,385,(2004).14. S.K. Tanielyan, R.L. Augustine, I. Prakash, K. Furlong and H.E. Jackson, Thisvolume.15. R.A. Sheldon, In Dioxygen Activation and Homogeneous Catalytic Oxidation,L.L. Simandi, Ed., Elsevier, Amsterdam, 1991, p. 573.16. S.S. Kim, H.C. Jung, Synthesis, 14, 2135, (2003)17. P. Gamez, I.W.C.E. Arends, J. Reedijk,; R.A. Sheldon, Chem. Commun., 19,2414-2415, (2003)18. T. Inokuchi, K. Nakagawa, S. Torii, Tetrahedron Letters, 36, 3223.19. A. Dijksman, A. Marino-Gonzalez, A.M. Payeras, I.W.C.E. Arends, R.A.Sheldon, J. Am. Chem.Soc., 123, 6826, (2001)20. A. Cecchetto, F. Fontana, F. Minisci, F. Recupero, Tetrahedron Letters, 42,6651, (2001)21. R. Liu, X. Liang, C. Dong, X. Hu, J. Am. Chem. Soc., 126, 4112, (2004).22. S.K. Tanielyan, R.L. Augustine, I. Prakash, K.E. Furlong, H.E. Jackson, PCTInt. Appl. WO 2005082825 (2005).23. S.K. Tanielyan, R.L. Augustine, O. Meyers, M. Korell, U.S. Pat. Appl. (2004).24. R. Augustine, S Tanielyan, Chemical Industries (Dekker), 89, (Catal. Org.React.), 73 (2003).
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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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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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Page 113 and 114: 86Phenol BenzoylationThis does not
Page 116: II. Symposium on Catalytic Oxidatio
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Page 127 and 128: 100 Propylene Partial OxidationThe
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Page 131 and 132: 104 Propylene Partial Oxidation0.01
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Page 137 and 138: 110Oxidation of n-Pentanemethacryli
Page 139 and 140: 112Oxidation of n-PentaneFReqox1ox2
Page 141 and 142: 114Oxidation of n-Pentanethe presen
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Page 145 and 146: 118Oxidation of n-PentaneReferences
Page 147 and 148: 120TEMPO Oxidation of Alcoholsthe u
Page 149 and 150: 122TEMPO Oxidation of AlcoholsThe r
Page 151 and 152: 124TEMPO Oxidation of Alcoholsany d
Page 153 and 154: 126TEMPO Oxidation of Alcoholsconce
Page 155: 128TEMPO Oxidation of AlcoholsMNT :
Page 159 and 160: 132Aminoalcohols to Aminocarboxylic
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Page 175 and 176: 148CO OxidationP25 TiO 2 , respecti
Page 177 and 178: 150CO Oxidation0.02(a)21802110(b)21
Page 179 and 180: 152CO Oxidationcarboxylate species
Page 182 and 183: Yamauchi 15519. 2006 Murray Raney A
Page 184 and 185: Yamauchi 157transformation is schem
Page 186 and 187: Yamauchi 159The X-ray diffraction p
Page 188 and 189: Yamauchi 161was -0.0009, -0.0032 an
Page 190 and 191: Yamauchi 163shown in Fig. 12. It wa
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Page 195 and 196: 168Nitrobenzene Hydrogenationfurthe
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Page 199 and 200: 172Nitrobenzene HydrogenationThe co
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Page 203 and 204: 176Nitrobenzene Hydrogenation10. G.
Page 205 and 206: 178 Hydrogenation of Dehydrolinaloo
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180 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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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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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 357T
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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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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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Kocal 4455. J.J. Siirola, An Indust
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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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Riermeier et al. 461References1. I.
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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 48755. Acce
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Wolf, Seebald and Tacke 489100Norma
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Wolf, Seebald and Tacke 4911,88Figu
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Woods et al. 49356. Transition Meta
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Woods et al. 495Effect of oxidation
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Woods et al. 497
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Woods et al. 499removed the samples
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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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