New strategies for multiphase catalysis using supercritical carbon dioxide [Elektronische Ressource] / vorgelegt von Maurizio Solinas

Solinas

Informations

• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2004
• Nombre de lectures: 7
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

New Strategies for Multiphase Catalysis
using Supercritical Carbon Dioxide
Von der Fakultät für Mathematik, Informatik und Naturwissenschaften
der Rheinisch-Westfälischen Technischen Hochschule Aachen zur Erlangung des
akademischen Grades eines Doktors der Naturwissenschaften genehmigte Dissertation
vorgelegt von
Diplom-Chemiker
Maurizio Solinas
aus Sassari
Berichter: Universitätsprofessor Dr. Walter Leitner
Universitätsprofessor Dr. Peter Wasserscheid
Tag der mündlichen Prüfung: 18. Juni 2004
Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar.The experimental part of the work has been carried out at the Max-Planck-Institut für
Kohlenforschung in Mülheim an der Ruhr (November 2000 to June 2002) and at the Institut
für Technische und Makromolekulare Chemie RWTH-Aachen (July 2002 to August 2003), in
the reasearch group of Prof. Dr. Walter Leitner.
I would like to thank:
Prof. Dr. Walter Leitner
For the trust he gave me, the big freedom with the selection and treatment of the research
contents and the outstanding work conditions. Furthermore, I would like to thank him for the
possibility he gave me to present my results in numerous conferences and for the enviable
possibility to work in a strongly international team.
The former director of the "Max-Planck-Institut für Kohlenforschung"
Prof. Dr. Manfred T. Reetz
For the opportunity to work in such excellent and historical institute.
I would also like to thanks
Prof. Dr. Peter Wasserscheid
To have accepted to be the second referee for this thesis and for the excellent scientific
discussions we had about ionic liquids.Table of contents
Table of contents
1 Introduction..............................................................................................................6
1.1 Concepts of Green Chemistry ..................................................................................7
1.2 "Regulated" system for multiphase catalysis .........................................................11
1.3 Aim and scope of this thesis17
2 Catalysis in ionic liquid/carbon dioxide.................................................................19
2.1 Current Status of the field ......................................................................................20
2.2 Properties of supercritical fluids and ionic liquids.................................................24
2.2.1 Supercritical carbon dioxide ..................................................................................24
2.2.2 Ionic liquids............................................................................................................34
2.2.3 Properties of ionic liquids/carbon dioxide systems................................................44
2.2.3.1 Literature survey ....................................................................................................44
2.2.3.2 Physical chemical properties of IL/CO system studied in the present thesis. ......472
2.3 Nickel catalyzed hydrovinylation reaction ............................................................55
2.3.1 Background55
2.3.2 Activation, tuning, and immobilization of the Wilke's catalyst in IL/CO ............592
2.3.3 Low coordinating chiral aluminum salts as co-catalyst in the hydrovinylation
reaction...................................................................................................................72
2.4 Enantioselective iridium catalyzed hydrogenation ................................................75
2.4.1 Background ............................................................................................................75
2.4.2 Enantioselective hydrogenation of N-(1-phenylethylidene)aniline in IL/CO ......792
2.4.3 Hydrogenation of other substrates .........................................................................82
2.4.4 Catalyst recycling and continuous flow processing...............................................85
2.5 Summary ................................................................................................................88
3 Catalysis with PEG modified ligands/carbon dioxide ...........................................90
3.1 Background91
3.2 Synthesis of PEG-modified phosphines and their application as ligands in solvent-
free hydroformylation ............................................................................................94
3.3 Batch-wise recycling of the PEG-catalyst .............................................................98
3.4 Multipurpose cartridge of catalyst for a variety of substrates and reactions .......103
3.5 Summary ..............................................................................................................109
4 Conclusion ...........................................................................................................111
3Table of contents
5 Experimental section............................................................................................117
5.1 Batch wise hydrovinylation of styrene.................................................................118
5.2 On-line monitoring of the hydrovinylation of styrene .........................................119
5.3 Continuous flow hydrovinylation of styrene .......................................................120
5.4 Continuous flow hydrovinylation with various substrates...................................120
5.5 Synthesis and characterization of aluminum salts ...............................................121
5.6 Hydrovinylation of styrene with chiral aluminum salts as co-catalyst ................121
5.7 Synthesis of the imine substrates .........................................................................122
5.8 Hydrogenation of N-(1-Phenylethylidene)aniline and other imine substrates.....123
5.9 Batch-wise recycling of hydrogenation catalyst ..................................................124
5.10 High pressure NMR investigation........................................................................124
5.11 Continuous flow hydrogenation of imine ............................................................124
5.12 Hydrogenation of α-methyl stilbene....................................................................125
5.13 Hydrogenation with other P-N ligands ................................................................125
5.14 Preparation of MeOPEG PPh (average mw 918 g/mol)..................................126750 2
5.15 Preparation of Ph PPEG PPhw 1336 g/mol) ...............................1272 1000 2
5.16 Catalytic hydroformylation using ligand MeOPEG PPh : general procedure..127750 2
5.17ylation using ligand PPh PEG PPh .1282 1000 2
5.18 Catalytic hydrogenation using ligand MeOPEG PPh .......128750 2
5.19 Catalytic hydroboration using ligand MeOPEG PPh : general procedure .......129750 2
5.20 Recycling experiment with ligand MeOPEG PPh : hydroformylation ............129750 2
5.21e PPh : consecutive reactions ......130750 2
5.22e PPh : hydroformylation of different750 2
substrates..............................................................................................................131
6 References............................................................................................................132
7 Publications...........................................................................................................139
8 Curriculum Vitae...................................................................................................140
4List of abbreviations
[4MBP][BTA] = 4-methyl-1-butylpyridinium bis(trifluoromethylsulfonyl)imide
[Ac] = acetate
acac = acetylacetonate
ADMET = Acyclic Diene Metathesis
ATR = Attenuated Total Reflectance
BARF = tetrakis-3,5-bis(trifluoromethyl)-phenylborate
BINAP = 2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl
BINOL = 2,2'dihydroxy-1,1'-binaphthyl
[BMIM] = 1-Butyl-3-methylimidazolium salt
[BMIM][PF6] = 1-Butyl-3-methylimidazolium hexafluorophosphate
CESS = Catalysis and Extraction using Supercritical Solvent
cod = 1,5-cyclooctadiene
d = Critical Densityc
d = Reduced Densityr
[EMIM] = 1-Ethyl-3-methylimidazolium salt
FBS = Fluorous Biphasic System
HAPs = Hazardous Air Pollutants
hfacac = hexafluoroacetylacetonate
[HMIM] = 1-hexyl-3-methylimidazolium salt
[iBMIM] = 1-isobuthyl-3-methylimidazolium salt
ICP = Inductively Coupled Plasma
IL = Ionic Liquid
MEA imine = (2-ethyl-6-methyl-phenyl)-(2-methoxy-1-methyl-ethylidene)-amine
[MMIM] = 1,3-di-methylimidazolium salt
MOP-OMe = 2-Diphenylphosphino-2'-methoxy-1-1'-binaphthyl
nbd = norbornadiene
[OMIM] = 1-Octyl-3-methylimidazolium salt
P = Critical Pressurec
PEG = Poly(ethylene glycol)
[PMIM] = 1-Penthyl-3-methylimidazolium salt
P = Reduced Pressurer
RCM = Ring Closing Metathesis
RTIL = Room Temperature Ionic Liquid
SCF = Supercritical Fluid
SCW = Supercritical Water
SHOP = Shell Higher-Olefin Process
STP = standard temperature and pressure (1 atm at room temperature)
T = Critical Temperaturec
THF = Tetrahydrofurane
TOF = Turn Over Frequency
TON = Turn Over Number
TPP = triphenylphosphine
TPPTS = Trisulfonated triphenylphosphine
T = Reduced Temperaturer
TRPTC = Thermo-Regulated Phase Transfer Catalysis
VOCs = Volatile Organic Compounds
51 Introduc