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Falling et al. 335Normal operation gives about 99% conversion of 1 with selectivities ofapproximately 94% 2,5-DHF, 1% crotonaldehyde and 4.5% oligomer. The oligomerremoved by the ORU is disposed of by incineration. Typically the catalyst level inoligomer is 3.5% TOP18 and 0.5% TOT. In view of the high value of the product2,5-DHF, this level of catalyst loss is fully acceptable. Optimized laboratoryextraction conditions show 99.5% recovery of TOP18 and 99.9% recovery of TOTfrom the oligomer. Second generation phosphonium iodide catalysts underdevelopment show promise for further improvement in catalyst recovery and costsavings.ConclusionsA novel homogeneous process for the catalytic rearrangement of 3,4-epoxy-1-buteneto 2,5-dihydrofuran has been successfully developed and scaled-up to productionscale. A tri(n-alkyl)tin iodide and tetra-(n-alkyl)phosphonium iodide co-catalystsystem was developed which met the many requirements for process operation. Theproduction of a minor, non-volatile side product (oligomer) was the dominatingfactor in the design of catalysts. Liquid-liquid extraction provided the neededcatalyst-oligomer separation process.AcknowledgementsWe gratefully acknowledge P. L. Dotson for catalyst screening experiments, M. K.Moore for catalyst extraction studies, T. R. Nolen for valuable engineeringassistance, A. J. Robertson (Cytec Industries) for phosphonium iodide advice andsamples, and the many members of the Eastman EpB Project Team.References1. Current address: Department of Chemical Engineering, University of SouthCarolina, Columbia, SC, 29208.2. D. Denton, S. Falling, J. Monnier, J. Stavinoha, Jr. and W. Watkins, ChimicaOggi, 14, 17 (1996).3. S. N. Falling and B. L. Gustafson, US Pat. 4,962,210 to Eastman KodakCompany (1990).4. J. R. Monnier, U.S. Pat. 5,536,851 to Eastman Chemical Company (1996); J. R.Monnier and C. S. Moorehouse, U.S. Pat. 5,670,672 to Eastman ChemicalCompany (1997); T. R. Nolen, S. N. Falling, D. M. Hitch, J. L. Miller and D. L.Terrill, US Pat. 5,681,969 to Eastman Chemical Company (1997); J. R.Monnier, J. W. Medlin and Y.-J. Kuo, Appl. Catal. A, 194-195, 463 (2000).5. S. N. Falling and G. W. Phillips, U.S. Pat. 5,254,701 to Eastman KodakCompany (1993).6. W. A. Beavers, U.S. Pat. 5,945,549 to Eastman Chemical Company (1999).7. S. Liang, T. Price, T. R. Nolen, D. B. Compton and D. Attride, U.S. Pat.5,502,257 to Eastman Chemical Company (1996); S. Liang and T. Price, USPat. 5,504,245 to Eastman Chemical Company (1996).
336Rearrangement of 3,4-Epoxy-1-Butene to 2,5-Dihydrofuran8. V. P. Kurkov, US Pat. 3,932,468 to Chevron Research Company (1976); R. G.Wall and V. P. Kurkov, US Pat. 3,996,248 to Chevron Research Company(1976).9. M. Fischer, DE Offen. 3926147 to BASF AG (1989); J. R. Monnier, S. A.Godleski, H. M. Low, L. G. McCullough, L. W. McGarry, G. W. Phillips and S.N. Falling, US Pat. 5,082,956 to Eastman Kodak Company (1992).10. J. R. Monnier and P. J. Muelbauer, US Pats. 4,897,498 and 4,950,773 toEastman Kodak Company (1990); J. R. Monnier, J. W. Medlin and M. A.Barteau, J. Catal., 203, 362 (2001).11. J. L. Stavinoha, Jr. and J. D. Tolleson, US Pat. 5,117,012 to Eastman KodakCompany (1992); J. L. Stavinoha, Jr., J. R. Monnier, D. M. Hitch, T. R. Nolenand G. L. Oltean, US Pat. 5,362,890 to Eastman Chemical Company (1994).12. J. C. Matayabas, Jr. and S. N. Falling, US Pat. 5,434,314 to Eastman ChemicalCompany (1995); S. N. Falling, S. A. Godleski, P. Lopez-Maldonado, P. B.MacKenzie, L. G. McCullough and J. C. Matayabas, Jr., US Pat. 5,608,034 toEastman Chemical Company (1997); T. Kuo, E. E. McEntire, S. N. Falling, Y.-C. Liu and W. A. Slegeir, US Pat. 6,451,926 to Eastman Chemical Company(2002).13. A. Baba and T. Nozari, H. Matsuda, Bull. Chem. Soc. Japan, 60, 1552 (1987).14. D. B. Malpass, L. W. Fannin and J. J. Ligi, Organometallics-Sigma BondedAlkyls and Aryls, Kirk Othmer Encyclopedia of Chemical Technology, ThirdEdition, 1981, Volume 16, pp. 573-579.15. P. J. Smith, Chemistry of Tin, P. J. Smith, Ed., Blackie Academic &Professional, Thomson Science, London, Second Edition, 1998, pp. 431-435.16. G. W. Phillips, S. N. Falling, S. A. Godleski and J. R. Monnier, US Pat.5,315,019 to Eastman Chemical Company (1994).17. S. N. Falling and P. Lopez, US Pat. 5,693,833 to Eastman Chemical Company(1997).18. S. N. Falling, S. A. Godleski, L. W. McGarry and J. S. Kanel, US Pat. 5,238,889to Eastman Kodak Company (1993).19. M. Pereyre, J.-P. Quintard and A. Rahm, Tin in Organic Synthesis, Butterworths& Co. Ltd., London, 1987.20. J.-C. Pommier, B. Delmond and J. Valade, Tet. Lett., 5287 (1967).21. B. Delmond, J.-C. Pommier and J. Valade, J. Organomet. Chem., 50, 121(1973).22. T. C. Lo and J. Prochazka, Reciprocating Plate Extraction Columns, Handbookof Solvent Extraction, T. C. Lo, M. H. I. Baird and C. Hanson, Eds., KriegerPublishing Company, Malabar, Florida, 1991, pp. 373-389.23. D. Glatz and W. Parker, Enriching Liquid-Liquid Extraction, Chem. Eng.,November 2004, pp. 44-48.
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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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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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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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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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Ostgard et al. 231metal atoms. Thes
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Kuusisto, Mikkola and Salmi 23526.
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Kuusisto, Mikkola and Salmi 237100A
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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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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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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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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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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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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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482 Reductive AlkylationSince the p
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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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