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432Glycerol Hydrogenolysisexpense of LA as the polarity of the reaction medium decreases, and indeed theirrespective selectivities vary in opposite directions (Table 3).[GO], M1.41.210.80.60.40.20pre -1rxn0 1 2 3 4 5 6Time, hWater EtOH/Water i-PrOH/Water t-BuOH/Water PG/WaterFigure 2. GO Conversion in Solvent/Water Mixtures aa Reactions carried out on 100ml solution of 1M GO and 0.1M KOH for 4-6h in H 2 Oat 200ºC and 1000psig H 2 using 0.5g Ni/Re catalyst.PG Yield, %40353025201510500 1 2 3 4 5 6Time, hWater EtOH/Water i-PrOH/Water t-BuOH/WaterFigure 3. PG Yield in Solvent/Water Mixtures aa Reactions carried out on 100ml solution of 1M GO and 0.1M KOH for 6h at 200ºCand 1000psig H 2 using 0.5g Ni/Re catalyst.The lower GO conversion rate in water could arise via several conditions. If GOis competing for adsorption sites on the catalyst surface with solvents, it may do somore successfully against i-PrOH and t-BuOH than against water because the -OHgroups in GO are all less shielded than the ones in i-PrOH and t-BuOH. This isfurther supported by the low lactic acid yields of reactions run in these alcohols,
Marincean et al. 433suggesting that water (a strong competitor) is not present in the vicinity of thecatalyst in alcohol solvent. Second, the presence of PG clearly reduces reaction rate -water may be ineffective in removing product PG from the reaction environment,whereas alcohols may preferentially displace PG from the carbon pore structure.Finally, water is a poor solvent for hydrogen, as hydrogen solubility in water is only20 to 30% that in simple alcohols (12).Full replacement of water with organic solvents leads to further increases in theGO conversion and PG selectivity in the order water < EtOH < i-PrOH < t-BuOH(Figure 4). As one can see from Table 3, GO conversion almost doubles going fromEtOH to t-BuOH, and yield of PG (Figure 5) increases with conversion. Yet PGselectivity only increases modestly, while at the same time the LA and EGselectivities decrease. Taken together these experimental observations suggest thatwhile the pathway for LA formation becomes less important when little water ispresent, presumably aldol reactions remain accessible. Glyceraldehyde, the firstintermediate of GO hydrogenolysis, is known to be very reactive towards aldolcondensation in basic media (13). The lower carbon balances may be due to the tothe reactivity of the carbonyl compounds formed as intermediates towardcondensation reactions, resulting in higher molecular weight unsaturated compounds,consistent with the appearance of color in the reaction samples.Table 3. GO Hydrogenolysis in Different Solvents aSelectivity (%)Exp Solvent Conv(%) PG LA EG C Balance (%)1 Water 22.9 60.9 26.6 8.1 99.02 EtOH/Water 34.4 57.1 15.5 10.4 94.13 i-PrOH/Water 59.8 54.9 7.5 9.2 83.14 t-BuOH/Water 57.6 61.5 7.6 8.0 86.85. PG/Water 10.8 n/a 46.2 9.2 95.26. EtOH 50.8 45.0 5.5 8.1 79.07. i-PrOH 66.7 69.3 3.1 8.9 87.58. t-BuOH b 89.9 58.2 1.2 5.6 68.69. 1,4-Dioxane b 54.5 22.8 0.0 14.4 65.8a Reactions carried out for 4-6h at 200ºC and 1000psig H 2 using 0.5g Ni/Re catalyst,0.1M KOH, and 1.0M GO. b 1.5 g water was added to the reaction solution toenhance KOH solubility.The experiment with 1,4-dioxane as solvent was characterized by poor solubilityof GO and KOH into the solvent, hence water was added to the initial mixture. Theabsence of the hydroxyl functionality in the solvent significantly decreased thesystem’s reactivity. The overall conversion and reactivity in this medium wasintermediate, but interesting is that (a) no LA was formed and (b) the selectivitytoward EG was substantially higher than in any other solvents.
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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. 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. 265pre-define the
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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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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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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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Page 455 and 456: Marincean et al. 429Experimental Se
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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.
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Page 495 and 496: 468 Chiral 2-Amino-1-Phenylethanola
Page 497 and 498: 470 t-Butanol DehydrationResults an
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Page 502 and 503: Pohlmann et al 47553. Leaching Resi
Page 504 and 505: Pohlmann et al 477this study. In th
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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. 495Effect of oxidation
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Woods et al. 497
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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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