Catalysis of Organic..

More documents

Recommendations

Info

Margitfalvi et al. 307Table 1. Variables and their levels in a simple optimization task.VariablesVariable levelsCatalyst 1, amount, g 0.05 0.10 0.15 0.20 0.25Catalyst 2, amount, g 0.00 0.05 0.10 0.15 0.20Hydrogen pressure, bar 25 50 75 100 125Temperature , o C 80 90 100 115 130Substrate concentration, M 0.08 0.15 0.30 0.60 0.90Stirring rate, rpm LOW HIGHTable 2. Modifiers used in selective hydrogenation or related reactions.Modifier Reaction TypeTransition metals (Pb) Triple bond M – CTransition metal salts Various M - CTransition metal oxides Various S – CQuinoline and analogues Dienes M – PTertiary amines Keto groups M – PNH 3 Reductive amination PTrialkyl and triaryl hydrofromylationM – PphosphinesAlkali hydroxides and Nitrile hydrogenation S – CcarbonatesLong chain amides For unsaturated nitriles M-PH 3 PO 3 and H 3 PO 4 Reductive aminationunsaturated compoundsof M-PSulfur containing Selective hydrogenation M-Ccompounds (CS 2 ,tiophene)Metal acetyl-acetonates Selective hydrogenation M-PMetal alkyls (SnR 2 Cl 2 ,) Nitrile hydrogenation M-CMetal (Sn, Ge) tetraalkyls Unsaturated aldehydes M-CCO Triple bond M-PChiral moieties Prochiral ketones, imines M-C, M-PAlkali and alkali earth Selective hydrogenation of M-CmetalsphenolVO x Reductive amination of M-PketonesM - modifier for the metal, S - modifier for the support, C - Compositional, P -Process.The above list of modifiers unambiguously shows their large diversity. There areexamples indicating that the best results can be achieved by combination of severalmodifiers [22]. Consequently, catalyst modification is an excellent field forcombinatorial research provided a library optimization method is available.
308 Catalyst Library DesignBasic Principle of HRSThe Holographic Research Strategy (HRS) developed for catalyst library design andoptimization can be considered as a deterministic approach, i.e. the route ofoptimization is unequivocally determined by the applied setting parameters [23,24]. InHRS similarly to other methods, such as the genetic algorithm (GA) [11]], the testresults of the (n-1) th generation is used to design the n th generation. During theoptimisation, the Holographic Research Strategy uses the rank between catalyststested. This rank is usually called as an “elite list” which is used to design the nextcatalyst generation.In HRS the key setting parameters are as follows [23,24]: (i) the total number ofexperimental variables, (ii) the selected levels of experimental variables, (iii) initialarrangement of variables along the axes (see Fig. 1) and the way of variable positionchanges, (iv) the number of the best hits around which the new catalyst generation iscreated, and (v) the size and the form of the experimental regions used to design thenext catalyst generation.Undoubtedly all of these parameters can influence both the rate and the certaintyof optimum search. In this respect the importance of the size of the experimentalregion has already been discussed in our previous studies [23,24].When all compositional variables have been selected the next task is the definitionof the levels of these variables. The levels can be given either in absoluteconcentration or as a relative ratio. The necessary number of levels for a variable is thearbitrary decision of the experimenter. It depends on the range that has to be explored.Special attention has to be devoted to possible non-smooth areas. In a reasonablynarrow range the effect of a variable are usually investigated using 4 – 5 levels, whichaccording to our results proved to be sufficient. In an eight-dimensional experimentalspace containing 78,000 – 125,000 possible compositions less than 150-200measurements were sufficient to find or approach the optimum [23,24].The levels of the compositional variables strongly depend on the role of the givencomponent in the catalyst composition. For key components steps in 0.5 w % is verycommon. For compositional modifiers of the active metal small steps has to be used in0.05 or 0.1 w % interval. For the determination of the required amount of processmodifiers (quinoline, amides, sulfur) the dispersion (D) of the key metal has to bedetermined or estimated. The amount of this type of modifiers (M) is usually in therange of 0.05-0.2 M mod /A metal where M mod = amount of the modifier in moles and Ametal is the total amount metal in gram atoms. The amount of modifiers for the supportcan be one order higher than the metal content of the catalyst.According to the above considerations if the optimization is performed underfixed process parameters the initial step in library design is finished, i.e. the catalystsof the initial library can be introduced into the experimental hologram. However, it isstrongly recommended to include one or two process parameters into the librarydesign procedure. Reaction temperature and hydrogen pressure is the two mostimportant process parameters influencing both the activity and the reactivity.
Page 2:
Catalysis ofOrganic Reactions
Page 5 and 6:
14. Catalyst Manufacture: Laborator
Page 7 and 8:
62. Catalysis of Organic Reactions,
Page 9 and 10:
108. Metal Oxides: Chemistry and Ap
Page 11:
CRC PressTaylor & Francis Group6000
Page 14:
xiii14. The Transformation of Light
Page 18 and 19:
xviien Catalisis y Petroquimica (UN
Page 20:
xix56. Transition Metal Removal fro
Page 24:
xxiiiChronology of Organic Reaction
Page 27 and 28:
To Zsuzsanna and Tim
Page 30 and 31:
Jones et al. 31. On the Use of Immo
Page 32 and 33:
Jones et al. 5three-phase tests in
Page 34 and 35:
Jones et al. 7In the HKR of rac-epi
Page 36 and 37:
Jones et al. 9term performance char
Page 38 and 39:
Jones et al. 115. A. S. Gruber, D.
Page 40 and 41:
Moses et al. 132. Supported Re Cata
Page 42 and 43:
Moses et al. 15perrhenate, followed
Page 44 and 45:
Moses et al. 17SnCOSnMe 4≡SiOReO
Page 46 and 47:
Moses et al. 19(AlOSi) of the cube.
Page 48 and 49:
Moses et al. 212.510 3 k obs / s -1
Page 50 and 51:
Wang et al. 233. Catalytic Hydrogen
Page 52 and 53:
Wang et al. 25The rate expressions
Page 54 and 55:
Wang et al. 27Schiff’s base forma
Page 56:
Wang et al. 29AcknowledgementsWe gr
Page 59 and 60:
32Halophosphite LigandsIn 1970, Pru
Page 61 and 62:
34Halophosphite LigandsThe ligands,
Page 63 and 64:
36Halophosphite LigandsTable 2 Temp
Page 65 and 66:
38Halophosphite Ligands3. P. W. N.
Page 67 and 68:
40Monolithic Bioreactorstrength for
Page 69 and 70:
42Monolithic BioreactorMenten equat
Page 72 and 73:
Gőbölös et al. 456. Highly Selec
Page 74 and 75:
Gőbölös et al. 47was practically
Page 76 and 77:
Gőbölös et al. 49noteworthy that
Page 78 and 79:
Gőbölös et al. 51Figure 2 NMR sp
Page 80:
Gőbölös et al. 53internal TMS in
Page 83 and 84:
56Hydrotalcite-like Catalysts[A n-
Page 85 and 86:
58Hydrotalcite-like Catalystssample
Page 88 and 89:
Mantilla, Tzompantzi, Torres and G
Page 90 and 91:
Page 92:
Page 95 and 96:
68Synthesis of MIBKwe examined the
Page 97 and 98:
70Synthesis of MIBK1412Conversion (
Page 99 and 100:
72Synthesis of MIBK4,4’-dimethyl
Page 101 and 102:
74Synthesis of MIBKobtained for MIB
Page 104 and 105:
Ardizzi et al. 7710. The Control of
Page 106 and 107:
Ardizzi et al. 79type acidity at th
Page 108:
Ardizzi et al. 81procedure describe
Page 111 and 112:
84Phenol Benzoylationconsecutive Fr
Page 113 and 114:
86Phenol BenzoylationThis does not
Page 116:
II. Symposium on Catalytic Oxidatio
Page 119 and 120:
92Oxidation with Microchannel Immob
Page 121 and 122:
Page 123 and 124:
Page 125 and 126:
Page 127 and 128:
100 Propylene Partial OxidationThe
Page 129 and 130:
102 Propylene Partial OxidationSiO
Page 131 and 132:
104 Propylene Partial Oxidation0.01
Page 133 and 134:
106 Propylene Partial Oxidation0.02
Page 135 and 136:
108 Propylene Partial OxidationRefe
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
Page 143 and 144:
116Oxidation of n-PentaneIn the mec
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 and 156:
128TEMPO Oxidation of AlcoholsMNT :
Page 157 and 158:
130TEMPO Oxidation of Alcoholsuptak
Page 159 and 160:
132Aminoalcohols to Aminocarboxylic
Page 161 and 162:
Page 163 and 164:
Page 165 and 166:
Page 167 and 168:
Page 169 and 170:
142Bromine-Free TEMPO-Based Catalys
Page 171 and 172:
Page 173 and 174:
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
Page 192:
Yamauchi 165These fine particles we
Page 195 and 196:
168Nitrobenzene Hydrogenationfurthe
Page 197 and 198:
170Nitrobenzene Hydrogenationhydrog
Page 199 and 200:
172Nitrobenzene HydrogenationThe co
Page 201 and 202:
174Nitrobenzene HydrogenationHence
Page 203 and 204:
176Nitrobenzene Hydrogenation10. G.
Page 205 and 206:
178 Hydrogenation of Dehydrolinaloo
Page 207 and 208:
Page 209 and 210:
Page 211 and 212:
Page 213 and 214:
Page 215 and 216:
188Modeling Mass Transfer Hydrogena
Page 217 and 218:
Page 219 and 220:
Page 221 and 222:
Page 223 and 224:
Page 225 and 226:
198 Fructose HydrogenationHOHCCH 2O
Page 227 and 228:
200 Fructose HydrogenationTable 1.
Page 229 and 230:
202 Fructose Hydrogenationmmol form
Page 231 and 232:
204 Fructose Hydrogenationthe subst
Page 233 and 234:
206 Fructose Hydrogenationcleave th
Page 235 and 236:
208 Fructose Hydrogenationfulfills
Page 237 and 238:
210 Fructose Hydrogenationis not th
Page 240 and 241:
Disselkamp et al. 21324. Cavitating
Page 242 and 243:
Disselkamp et al. 215column. In a p
Page 244 and 245:
Disselkamp et al. 217selectivity es
Page 246 and 247:
Disselkamp et al. 219hydrogenated (
Page 248 and 249:
Disselkamp et al. 221A somewhat mor
Page 250 and 251:
Disselkamp et al. 223Scheme 4.cis-2
Page 252 and 253:
Disselkamp et al. 225conventional c
Page 254 and 255:
Ostgard et al. 22725. The Treatment
Page 256 and 257:
Ostgard et al. 229Table 1. The reac
Page 258 and 259:
Ostgard et al. 231metal atoms. Thes
Page 260 and 261:
Ostgard et al. 233In conclusion, th
Page 262 and 263:
Kuusisto, Mikkola and Salmi 23526.
Page 264 and 265:
Kuusisto, Mikkola and Salmi 237100A
Page 266:
Kuusisto, Mikkola and Salmi 2399. B
Page 269 and 270:
242 1-Phenyl-1-Propyneof cis-β-met
Page 271 and 272:
244 1-Phenyl-1-Propynealkene. When
Page 274 and 275:
Musolino, Apa, Donato and Pietropao
Page 276 and 277:
Page 278 and 279:
Page 280 and 281:
Gőbölös and Margitfalvi 25329. R
Page 282 and 283:
Gőbölös and Margitfalvi 255maxim
Page 284: Gőbölös and Margitfalvi 257Y=421
Page 288 and 289: Rothenberg et al. 26130. How to Fin
Page 290 and 291: Rothenberg et al. 263By dividing th
Page 292 and 293: Rothenberg et al. 265pre-define the
Page 294 and 295: Rothenberg et al. 267Table 1. Parti
Page 296 and 297: Rothenberg et al. 269Experimental S
Page 298 and 299: Angueira and White 27131. Novel Chl
Page 300 and 301: Angueira and White 273optimizedgeom
Page 302 and 303: Angueira and White 275F igure 4 - c
Page 304 and 305: Angueira and White 277Table 1. 27 A
Page 306 and 307: Angueira and White 279obtained from
Page 308 and 309: Robitaille, Clément, Chapuzet and
Page 316 and 317: Cao, White, Wang and Frye 28933. Se
Page 318: Cao, White, Wang and Frye 291Experi
Page 321 and 322: 294Chiral Ferrocene Ligandsnew Twin
Page 323 and 324: 296Chiral Ferrocene LigandsTable 1.
Page 325 and 326: 298Chiral Ferrocene Ligandsprevents
Page 327 and 328: 300Chiral Ferrocene LigandsConclusi
Page 329 and 330: 302Chiral Ferrocene Ligandsextracte
Page 331 and 332: 304 Catalyst Library DesignIn gas p
Page 333: 306 Catalyst Library Designd−(b 0
Page 337 and 338: 310 Catalyst Library DesignD in com
Page 339 and 340: 312 Catalyst Library DesignCatalyst
Page 341 and 342: 314 Catalyst Library Design27. S. H
Page 343 and 344: 316 Dendrimer TemplatesWe are devel
Page 345 and 346: 318 Dendrimer TemplatesThe differen
Page 347 and 348: 320 Dendrimer TemplatesWe encounter
Page 349 and 350: 322 Dendrimer TemplatesThe 100 cm -
Page 352: V. Symposium on Acid and Base Catal
Page 355 and 356: 328Rearrangement of 3,4-Epoxy-1-But
Page 365 and 366: 3382,5-Dimethyl-2,4-Hexadieneharves
Page 367 and 368: 3402,5-Dimethyl-2,4-Hexadienestabil
Page 369 and 370: 3422,5-Dimethyl-2,4-Hexadiene10086Y
Page 371 and 372: 3442,5-Dimethyl-2,4-Hexadienereacti
Page 373 and 374: 3462,5-Dimethyl-2,4-Hexadiene8. www
Page 375 and 376: 348Heteropoly AcidsSOOO O+ +OS1 2 3
Page 377 and 378: 350Heteropoly AcidsTable 3. Acylati
Page 379 and 380: 352Heteropoly AcidsSiO 2 is the bes
Page 382 and 383: Diez, Di Cosimo and Apesteguia 3554
Page 384 and 385:
Diez, Di Cosimo and Apesteguia 357T
Page 386 and 387:
Diez, Di Cosimo and Apesteguia 359A
Page 388 and 389:
Diez, Di Cosimo and Apesteguia 361I
Page 390 and 391:
Diez, Di Cosimo and Apesteguia 3630
Page 392 and 393:
O’Keefe, Jiang, Ng and Rempel 365
Page 394 and 395:
Page 396 and 397:
Page 398 and 399:
Page 400 and 401:
Page 402:
VI. Symposium on “Green” Cataly
Page 405 and 406:
378 Polyurethane from Natural OilMe
Page 407 and 408:
380 Polyurethane from Natural Oilco
Page 409 and 410:
382 Polyurethane from Natural Oilfr
Page 411 and 412:
384 Polyurethane from Natural OilTh
Page 413 and 414:
386 Carbonylation of Chloropinacolo
Page 415 and 416:
Page 417 and 418:
Page 419 and 420:
Page 421 and 422:
Page 423 and 424:
396 Recycling Homogeneous Catalysts
Page 425 and 426:
Page 427 and 428:
Page 429 and 430:
Page 431 and 432:
Page 433 and 434:
406“Green” Catalysts for Biodie
Page 435 and 436:
Page 437 and 438:
Page 439 and 440:
Page 441 and 442:
Page 443 and 444:
416 Production of BiodieselTable 1.
Page 445 and 446:
418 Production of Biodieselto a mas
Page 447 and 448:
420 Production of BiodieselEthyl st
Page 449 and 450:
422 Production of Biodiesel10080Sel
Page 451 and 452:
424 Production of Biodieselproduct
Page 453 and 454:
Marincean et al. 42747. Glycerol Hy
Page 455 and 456:
Marincean et al. 429Experimental Se
Page 457 and 458:
Marincean et al. 431neutralize all
Page 459 and 460:
Marincean et al. 433suggesting that
Page 461 and 462:
Marincean et al. 435increasing from
Page 464 and 465:
Kocal 43748. Developing Sustainable
Page 466 and 467:
Kocal 439description of the four st
Page 468 and 469:
Kocal 441metallurgy in parts of the
Page 470 and 471:
Kocal 443that capital investment co
Page 472:
Kocal 4455. J.J. Siirola, An Indust
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
Page 482 and 483:
Riermeier et al. 45550. catASium ®
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 520 and 521:
Woods et al. 49356. Transition Meta
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
show all

Catalysis of Organic..

Create successful ePaper yourself

Delete template?

Save as template?