Microwave assisted synthesis of monomeric and polymeric amides: kinetics and mechanistic considerations [Elektronische Ressource] / vorgelegt von Mauro Iannelli

Informations

• Publié par: heinrich-heine-universitat_dusseldorf
• Publié le: 01 janvier 2006
• Nombre de lectures: 31
• Langue: Deutsch
• Poids de l'ouvrage: 3 Mo

Extrait

MICROWAVE-ASSISTED SYNTHESIS
OF
MONOMERIC AND POLYMERIC AMIDES:

KINETICS AND MECHANISTIC CONSIDERATIONS




Inaugural-Dissertation

zur

Erlangung des Doktorgrades der

Mathematisch-Naturwissenschaftlichen Fakultät

der Heinrich-Heine-Universität Düsseldorf


vorgelegt von


Mauro Iannelli

aus

Benevento


Dezember 2006
I
Aus dem Institut für Präparative Polymerchemie
der Heinrich-Heine Universität Düsseldorf















Gedruckt mit der Genehmigung der
Mathematisch-Naturwissenschaftlichen Fakultät der
Heinrich-Heine-Universität Düsseldorf





Referent: Prof. Dr. H. Ritter

Koreferent: Prof. Dr. C. Staudt

Tag der mündlichen Prüfung: 24.01.2007

II


Psalm 23

A psalm of David.

1 The LORD is my shepherd, I shall not be in want.

2 He makes me lie down in green pastures, He leads me beside quiet waters,

3 He restores my soul. He guides me in paths of righteousness for his name's sake.






Alla mia famiglia
III
Contents
ABSTRACT.......................................................................................................................................................................1
PREFACE AND AIM ......................................................................................................................................................3
1 MICROWAVE CHEMISTRY ....................................................................................................................................4
1.1 INTRODUCTION .......................................................................................................................................4
1.2 MICROWAVE HEATING ..........................................................................................................................5
1.2.1 DIELECTRIC HEATING..........................................................................................................................7
1.2.2 CONDUCTION HEATING.......................................................................................................................9
1.3 THE TEMPERATURE ISSUE ...................................................................................................................10
1.3.1 “ATYPICAL” THERMOMETERS ..........................................................................................................10
1.3.2 FLUOROPTIC THERMOMETERS..........................................................................................................11
1.3.3 INFRARED PYROMETERS ...................................................................................................................11
1.3.4 THERMOCOUPLES..............................................................................................................................13
1.4 MICROWAVE REACTORS......................................................................................................................14
1.4.1 SINGLE-MODE REACTORS .................................................................................................................15
1.4.2 MULTIMODE REACTORS....................................................................................................................16
1.5 MICROWAVE EFFECTS..........................................................................................................................18
1.5.1 THERMAL MICROWAVE EFFECTS......................................................................................................18
1.5.2 SPECIFIC MICROWAVE EFFECTS........................................................................................................19
1.6 MICROWAVE PROCESSING TECHNIQUES ............................................................................................21
1.6.1 SOLVENT-FREE REACTIONS ..............................................................................................................21
1.6.2 PHASE-TRANSFER CATALYSIS ..........................................................................................................22
1.6.3 REACTIONS USING SOLVENTS...........................................................................................................23
1.7 REFERENCES .........................................................................................................................................25

2 SYNTHESIS AND POLYMERIZATION OF CHIRAL (METH)ACRYLAMIDES ..................................... 27
2.1 INTRODUCTION AND LITERATURE SURVEY........................................................................................27
2.2 BULK SYNTHESIS AND ONE-POT POLYMERIZATION OF (R)-N-(1-
PHENYLETHYL)METHACRYLAMIDE ...........................................................................................................29
2.3 DIRECT SYNTHESIS AND POLYMERIZATION OF (R)-N-(1-PHENYLETHYL)ACRYLAMIDE.................37
2.4 EXPERIMENTAL.....................................................................................................................................44
2.4.1 SYNTHESIS OF (R)-N-(1-PHENYL-ETHYL)-METHACRYLAMIDE (3) UNDER MW IRRADIATION....44
2.4.3 SYNTHESIS OF THE POLYMER POL 1.................................................................................................45
2.4.4 SYNTHESIS OF (R)-N-(1-PHENYLETHYL)-ACRYLAMIDE (8) ...........................................................46
2.4.5 SYNTHESIS OF THE POLYMERS P1-P5 ..............................................................................................46
IV
2.4.6 SYNTHESIS OF THE POLYMER P6 BY THERMAL HEATING IN OIL-BATH .........................................47
2.5 REFERENCES .........................................................................................................................................47

3 AMIDATION OF POLY(ETHYLENE-CO-ACRYLIC ACID) ......................................................................... 49
3.1 INTRODUCTION AND LITERATURE SURVEY........................................................................................49
3.2 RESULTS AND DISCUSSIONS ................................................................................................................51
3.3 EXPERIMENTAL.....................................................................................................................................61
3.3.1 SYNTHESIS OF P1...............................................................................................................................61
3.3.2 ELECTRIC CONDUCTIVITY MEASUREMENTS....................................................................................61
3.4 REFERENCES .........................................................................................................................................62

4 IMIDIZATION REACTIONS ................................................................................................................................. 63
4.1 INTRODUCTION AND LITERATURE SURVEY........................................................................................63
4.2 SYNTHESIS OF N-BENZENSULFONAMIDE MALEIMIDE........................................................................64
4.3 POLYMERIZATION OF N-BENZENSULFONAMIDE MALEIMIDE............................................................67
4.4 SYNTHESIS OF 2-HYDROXY-N-(2-HYDROXYPROPANOYL)-N-(1-PHENYLETHYL)PROPANAMIDE ...70
4.5 EXPERIMENTAL.....................................................................................................................................73
4.5.1 SYNTHESIS OF 4-(2,5-DIOXO-2,5-DIHYDRO-PYRROL-1-YL)-BENZENSULFONAMIDE (3). .............73
4.5.2 POLYMERIZATION OF 4-(2,5-DIOXO-2,5-DIHYDRO-PYRROL-1-YL)-BENZENSULFONAMIDE (3)...73
4.5.3 SYNTHESIS OF 2-HYDROXY-N-(2-HYDROXYPROPANOYL)-N-(1-PHENYLETHYL)PROPANAMIDE
(9). ...............................................................................................................................................................74
4.6 REFERENCES .........................................................................................................................................75

5 FREE RADICAL POLYMERIZATION................................................................................................................ 76
5.1 INTRODUCTION AND LITERATURE SURVEY........................................................................................76
5.2 POLYMERIZATION OF ACRYLIC MONOMERS......................................................................................77
5.3 EXPERIMENTAL.....................................................................................................................................81
5.4 REFERENCES .........................................................................................................................................82

6 CONCLUSIVE MECHANISTIC CONSIDERATIONS ..................................................................................... 83

7 EXPERIMENTAL NOTES ..........................................................................................