3,3- and 4,4'-dimethoxy-2,2'-bipyrroles and aminopyrroles with high level electrons [Elektronische Ressource] : syntheses and properties of new poly-(2,2'-bipyrroles) / vorgelegt von Sergiy Anikin

Informations

• Publié par: universitat_regensburg
• Publié le: 01 janvier 2004
• Nombre de lectures: 24
• Langue: Deutsch
• Poids de l'ouvrage: 1 Mo

Extrait

3,3- and 4,4’-Dimethoxy-2,2’-bipyrroles
and Aminopyrroles with high level
electrons





Syntheses and Properties of new Poly-(2,2’-bipyrroles)










Dissertation
zur Erlangung des Doktorgrades (Dr. rer. nat.)
der Fakultä t f r Chemie und Pharmazie der Universitä t Regensburg








vorgelegt
von Sergiy Anikin
aus Odessa
2004
ü































Promotionsgesuch eingereicht am: 24. Juni 2004
Promotionskolloquium
voraussichtlich am: 12. Juli 2004
Anleitung zur Dissertation: Prof. Dr. Andreas Merz
Prü fungsausschuß: Prof. Dr. Gottfried Märkl (Vorsitzender)
Prof. Dr. Albrecht Mannschreck (1. Gutachter) Prof. Dr. Jörg Daub (2. Gutachter) Prof. Dr. Henri Brunner (3. Prü fer)
Die vorliegende Arbeit entstand in der Zeit von Dezember 2000 bis Juni 2004 an der
Fakultä t für Chemie und Pharmazie der Universitä t Regensburg.







Sehr herzlich bedanken möchte ich mich bei meinem Doktorvater


Herrn Prof. Dr. Andreas Merz

f r die interessante Themenstellung, sein ständiges Interesse am Fortgang dieser Arbeit,
sowie die Erm glichung zur Teilnahme an verschiedenen Tagungen und Konferenzen.






Herrn Prof. Dr. Oliver Reiser danke ich für die Bereitstellung seiner Laboratorien und dem
angenehmen Betrieb an seinem Lehrstuhl.
ö
üContents


C O N T E N T S


I. INTRODUCTION...........................................................................................................1
1.1 P YRROLE PRESENCE IN THE NATURE...........................................................................1
1.2 A PPLICATION OF PYRROLES........................................................................................3
1.3 C ONDUCTING POLYMERS............................................................................................5
1.4 P ROBLEM DEFINITION.................................................................................................8
II. SYNTHESES OF PYRROLES AND BIPYRROLES................................................9
2.1 G ENERAL PREPARATION METHODS OF PYRROLES.......................................................9
HANTZSCH PYRROLE SYNTHESIS ..............................................................................10
KNORR PYRROLE SYNTHESIS ....................................................................................10
PAAL-KNORR PYRROLE SYNTHESIS ..........................................................................11
SYNTHESIS OF 3,4-ALKOXYPYRROLES......................................................................12
SYNTHESIS OF 3-ALKOXYPYRROLES.........................................................................13
MOMOSE ROUTE TOWARDS 3-HYDROXYPYRROLES ..................................................14
MODIFIED KNORR PYRROLE SYNTHESIS ...................................................................15
2.2 P ROTECTING AT THE PYRROLE NITROGEN.................................................................16
2.3 REPARATION OF THE PYRROLE FOR CARBON-CARBON COUPLING REACTIONS.........19
2.3.1 S IDE REACTION................................................................................................20
2.4 P YRROLE COUPLINGS REACTIONS............................................................................23
2.4.1 C ROSS-COUPLING REACTIONS ........................................................................23
2.4.2 N EGISHI – COUPLING ......................................................................................24
2.4.3 S TILLE – COUPLING ........................................................................................25
2.4.4 T HE ULLMANN – COUPLING.26
2.4.5 K AUFFMANN-COUPLING .................................................................................27
2.5 S YNTHESIS OF 3-ALKOXYPYRROLES, 3,3’-DIMETHOXY-2,2’-BIPYRROLE AND 4,4’-
DIALKOXY-2,2’-BIPYRROLES....................................................................................29 Contents
2.5.1 S YNTHESIS OF 3-ALKOXYPYRROLES ................................................................29
2.5.2 4,4’-DIALKOXY-2,2’-BIPYRROLES ...................................................................35
2.5.3 3,3’-DIMETHOXY-2,2’-BIPYRROLE.38
2.6 S YNTHESES OF 3-METHOXY-4-AMINOPYRROLES........................................................41
2.7 S YNTHESIS OF 3,4-DIAMINOPYRROLES.......................................................................44
III. ELECTROCHEMICAL EXPERIMENTS...............................................................47
3.1 A SHORT INTRODUCTION INTO THE CYCLIC VOLTAMMETRY TECHNIQUE .................47
3.2 P OLYMERISATION MECHANISM .................................................................................49
3.3 E LECTROCHEMICAL CHARACTERISATION OF 3- AND 3,4-ALKOXY SUBSTITUTED
PYRROLES .................................................................................................................52
3.4 P OLYMER FILMS CONDUCTIVITY ...............................................................................64
3.4.1 C ONDUCTIVITY MEASUREMENTS .....................................................................65
SUMMARY........................................................................................................................73
V. EXPERIMENTAL PART............................................................................................77
5.1 A NALYTICAL AND SPECTRAL MEASUREMENTS..........................................................77
5.2 C HEMICALS, EQUIPMENT AND TECHNIQUE................................................................79
5.3 S YNTHESIS AND PROPERTIES OF ALKOXYPYRROLES..................................................81
5.3.1 P YRROLE RING FORMATION..............................................................................81
5.3.2 S YNTHESES OF PRECURSORS FOR RING COUPLING ............................................88
5.3.3 B IPYRROLE SKELETON SYNTHESIS ...................................................................93
5.3.4 P YRROLE- AND BIPYRROLE- CARBOXYLIC ACIDS.............................................96
5.3.5 T HERMIC DECARBOXYLATION........................................................................101
5.3.6 P YRROLE RING DEPROTECTION ......................................................................104
5.4 S YNTHESES AND PROPERTIES OF AMINOPYRROLES...................................................109
5.4.1 N ITROPYRROLE RING FORMATION..................................................................109
5.4.2 ITRO COMPOUNDS REDUCTION.....................................................................118
5.4.3 A MINO DERIVATIVES METHYLATION..............................................................121 Contents
VI. APPENDIX.............................................................................................................................123
VII. LITERATURE.....................................................................................................................137
VIII. ACKNOWLEDGEMENTS...............................................................................................143


Chapter 1












1.1 Pyrrole presence in the Nature

Pyrroles are widely distributed in the Nature. This five-membered heterocycle serves as a
Nature building block in chlorophylls (1) and haem (2); nucleic acids, the bile pigments,
the core of vitamin B , and many other biologically active compounds (also the 12
derivatives of tetrapyrrole) [1]. The pyrrole ring occurs in a number of naturally occurring
antibiotics (3), including the increasingly important netropsin (4). Furthermore, an indol
fragment, where the pyrrole ring is fused with benzene is incorporated in the aminoacid
triptophane, alkaloids (6) and in indigo (Figure 1.1).

It is also known that most of the naturally occurring organohalogen compounds are
produced by marine organisms, bacteria, fungi and terrestrial plants, but very few of them
were found in higher animals. Recently the presence of several halogenated bipyrroles was
discovered [2] (5) in the eggs of Pacific and Atlantic Ocean seabirds (Figure 1.1).
2 I. Introduction
OO
CO CH2 3 OH
H C3
NNH
FeN N
NNMg
N N
R HO C CO H2 2
1 2
Chlorophyll a and b Haemoglobin
R= CH , CHO3
HN
Br Br
OH NHH 2NN HBr
BrN OH
NH NH
N O CHBr 3NHN
O CH3NH Antibiotic netropsinA natural antibiotic 2
3 4
Br Br NCH3 O N
HH HN R
R ON
H
O OCH3 Br Br O
O O
O
O
Alkaloid reserpine R= Br, Cl
5 6

Figure 1.1 Pyrrole ring in the natural compounds
I. Introduction 3
1.2 Application of pyrroles

The derivatives of pyrrole have found a wide range of applications in the modern science
and technology.