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Gőbölös et al. 51Figure 2 NMR spectrum of the mixture of stereoisomers of esters.Figure 3 NMR spectrum of a mixture containing ~90% of trans-isomer of ester.In conclusion, 4-Amino-benzoicacid can be hydrogenated to 4-aminocyclohexanecarboxylic acid on 5wt.% Ru- and Rh/Al 2 O 3 catalysts with 100% yield in 2 wt. %NaOH-H 2 O at 80-100 °C, 10 MPa H 2, for 5h. However, the ratio of trans/cisstereoisomers of the product does not exceed a value of 1/1. Raw reaction mixture
52Preparation of 4-Aminocarboxylic Acidcan be further processed in the presence of a commercial Raney nickel catalyst at130 °C, 10 MPa H 2 for 5 h. In this alkali mediated isomerization the trans/cis isomerratio was 7/3. The cis isomer isolated by fractional crystallization, can be isomerizedon Raney® nickel catalysts in 2%NaOH-H 2 O at 120-140°C, 1 MPa H 2 for 5 h toobtain the trans isomer with a yield of ca. 70 %. The two-step synthesis resulted intrans-4-aminocyclohexane carboxylic acid with a yield above 90%. SPR16 (AMTECGmbH, Germany) high-throughput reactor system equipped with 16 mini autoclavesis useful for fast screening of liquid-phase catalytic reactions.Experimental SectionSupported catalysts were used for the hydrogenation of the aromatic ring of 4-aminobenzoicacidand its ethyl ester, whereas Raney® nickel was applied to catalyze thecis→trans isomerization of 4-amino-cyclohexane carboxylic acid.Catalysts: 5%Ru/Al 2 O 3 and 4%Rh/Al 2 O 3 catalysts were received from AirPoducts&Chemicals Co., whereas ESCAT 44 5%Ru/Al 2 O 3 (E44) and ESCAT 345%Rh/Al 2 O 3 (E34) catalysts were purchased from Engelhard. Co. ESCAT 105%Pd/C (E10), ESCAT 40 5%Ru/C (E40) and ESCAT 30 5%Rh/C (E30) catalystswere also purchased from Engelhard Co. Raney® nickel catalyst Metalyst-alpha-1301, and B113 W with nickel content of 35% and 90 %, respectively werepurchased from Degussa GmbH.Activity test: Catalyst screening and optimization of process parameters for bothsteps, i.e. aromatic ring saturation and stereo-isomerization, were performed using ahigh throughput (HT) fully automated batch reactor system equipped with 16 miniautoclaves(SPR16, AMTEC GmbH Germany). In the hydrogenation of the aromaticring the effect of catalyst, solvent and reaction temperature was investigated. In theisomerization step and the effect of reaction temperature (100-140 °C), hydrogenpressure (1-7 MPa) and the substrate/catalyst ratio was screened.Separation of cis/trans isomersThe separation of the stereoisomers was done by fractional crystallization modifyingthe method described in ref. (14). After filtering the catalyst and evaporating themajority of water ethanol was added and pure cis isomer was precipitated. Then theprecipitate was filtered and washed with the ethanol. After cooling the mother liquorthe cis isomer precipitate was removed again, and the solvent evaporation,precipitation, filtration and washing cycle was repeated twice.Analysis: Fast quality control of both the product of hydrogenation and stereoisomerizationand was done by thin layer chromatography (TLC) (15). The analysisof the hydrogenation product was done by using a mixtureCHCl 3 :CH 3 OH:NH 4 OH=5:5:1 for elution. o-Chloro-toluidine was used to developthe product 4-amino-cyclohexane carboxylic acid. The ratio of trans/cis isomers wasalso estimated by using TLC: Sil/G UV 254 , (detection at 254 nm) water for elution,and the same compound as developing agent. The ratio of trans/cis isomers ofselected samples was determined by 1 H-NMR analysis of the ester derivative of 4-amino-cyclohexane carboxylic acid. NMR spectra were taken in CDCl 3 at 30°Cusing a Varian Unity Inova 400 spectrometer. Chemical shifts are reported relative to
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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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Page 42 and 43: Moses et al. 15perrhenate, followed
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Page 52 and 53: Wang et al. 25The rate expressions
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Page 56: Wang et al. 29AcknowledgementsWe gr
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Page 67 and 68: 40Monolithic Bioreactorstrength for
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Page 74 and 75: Gőbölös et al. 47was practically
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Page 95 and 96: 68Synthesis of MIBKwe examined the
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Page 101 and 102: 74Synthesis of MIBKobtained for MIB
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Page 106 and 107: Ardizzi et al. 79type acidity at th
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Page 113 and 114: 86Phenol BenzoylationThis does not
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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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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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3402,5-Dimethyl-2,4-Hexadienestabil
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3422,5-Dimethyl-2,4-Hexadiene10086Y
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3442,5-Dimethyl-2,4-Hexadienereacti
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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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Diez, Di Cosimo and Apesteguia 3630
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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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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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