Functional aromatic amino ketones as UV/Vis probes for various liquid and solid environments [Elektronische Ressource] / vorgelegt von Mohamed El-Sayed

Sony Viao

Description

Functional Aromatic Amino Ketones as UV/Vis probes for various liquid and solid environments von der Fakultät für Naturwissenschaften der Technischen Universität Chemnitz genehmigte Dissertation zur Erlangung des akademischen Grades doctor rerum naturalium (Dr. rer. nat.) vorgelegt von Master in Chemie Mohamed El-Sayed geboren am 16.11.1966 in Port-Said, Ägypten eingereicht am 20 Dezember 2002 Gutachter: Prof. Dr. Stefan Spange, Technische Universität Chemnitz Prof. Dr. Heinrich Lang, Tecnitz Prof. Dr. Rainer Beckert, Friedrich-Schiller-Universität Jena Tag der Verteidigung: 1 April 2003 Bibliographische Beschreibung und Referat 2 El-Sayed, M. Functional Aromatic Amino Ketones as UV/Vis probes for various liquid and solid environments Technische Universität Chemnitz-Zwickau, Fakultät für Naturwissenschaften, Dissertation, 2003, 140 Seiten, 141 Literaturzitate, 35 Abbildungen, 24 Tabellen, 14 Diagramme. Zum gegenwärtigen Kenntnisstand bezüglich Solvatochromie, Sol-Gel Prozesse, und der Synthese von Polyketonen wird eine kurze Einführung gegeben. Die Synthese-konzeptionen funktionalisierter aromatischer Aminoketone werden vorgestellt. Die neuen Verbindungen wurden mittels Elementaranalyse, Röntgenstrukturanalyse, und spektroskopischen (NMR, UV/Vis, MS) Methoden aufgeklärt.

Informations

• Publié par: technische_universitat_chemnitz
• Publié le: 01 janvier 2003
• Nombre de lectures: 69
• Langue: Deutsch
• Poids de l'ouvrage: 1 Mo

Extrait

Functional Aromatic Amino Ketones as UV/Vis probes for

various liquid and solid environments

von der Fakultät für Naturwissenschaften der Technischen Universität Chemnitz genehmigte Dissertation zur Erlangung des akademischen Grades doctor rerum naturalium (Dr. rer. nat.) vorgelegt von Master in Chemie Mohamed El-Sayed geboren am 16.11.1966 in Port-Said, Ägypten eingereicht am 20 Dezember 2002 Gutachter: Prof. Dr. Stefan Spange, Technische Universität Chemnitz Prof. Dr. Heinrich Lang, Technische Universität Chemnitz Prof. Dr. Rainer Beckert, Friedrich-Schiller-Universität Jena

Tag der Verteidigung: 1 April 2003

Bibliographische Beschreibung und Referat

2

Bibliographische Beschreibung und Referat El-Sayed, M. Functional Aromatic Amino Ketones as UV/Vis probes for various liquid and solid environments Technische Universität Chemnitz-Zwickau, Fakultät für Naturwissenschaften, Dissertation, 2003, 140 Seiten, 141 Literaturzitate, 35 Abbildungen, 24 Tabellen, 14 Diagramme.  Zum gegenwärtigen Kenntnisstand bezüglich Solvatochromie, Sol-Gel Prozesse, und der Synthese von Polyketonen wird eine kurze Einführung gegeben. Die Synthese- konzeptionen funktionalisierter aromatischer Aminoketone werden vorgestellt. Die neuen Verbindungen wurden mittels Elementaranalyse, Röntgenstrukturanalyse, und spektroskopischen (NMR, UV/Vis, MS) Methoden aufgeklärt. Im Mittelpunkt der Untersuchungen steht die Untersuchung des Einflusses von unterschiedlichen Medien (Lösungmittel, Oberflächen, Sol-Gel Materialien und Nachbarnmoleküle im Kristall) auf die Lage der UV/Vis-Absorptionsmaxima verschiedener aromatischer Aminoketone. Die Ergebnisse der Untersuchungen liefern Informationen in Bezug auf der spezifische Solvotationsvermögen, die Polarität von Feststoffoberflächen, der Einfluss funktionaler Gruppen in aromatischen Aminoketonen auf die intermolekulare Wasserstoff- brückenbindungen in Kristallen, und über die Natur der Gast-Host- Wechselwirkungen.  Auf der Basis von nucleophilen Substitutionsreaktionen wurden zwei verschiedene Prozesse für die Synthese von Poly(benzophenone-co-piperazin) und der Kompositform entwickelt. Molekulare Strukturen und Eigenschaften konnten durch Elementaranalyse, mehrere spektroskopische (IR, Festkörper-NMR, UV/Vis, MALDI-TOF) Methoden, Zetapotentialmessungen in wässriger Phase und thermogravimetrischen Bestimmungen charakterisiert werden. Aromatische Aminoketonen, Aerosil 300, Sol-Gel-Prozess, Ormosile, Hybridmaterialien, Solvatochromie, Acidität, Basizität, Dipolarität/Polarisierbarkeit, intermolekulare Wasserstoffbrückenbindungen, Poly(benzophenone-co-piperazine).

Contents

Table of contents List of publications Acknowledgement Symbols and abbreviations IGeneral part 1.1 Introduction 1.2 Solvatochromism  1.2.1 Aromatic amino ketones  1.2.2 Related compound 1.3 Sol-gel process 1.4 Aromatic amino ketone polymers IIAim of this work IIIResults and discussion 3.1 Aromatic amino ketones

 3.1.1 UV/Vis absorption spectroscopy and linear solvation energy (LSE)

 relationships  3.1.1.1 Solvent effects on the UV/Vis absorption spectra  3.1.1.2 Mathematical calculations based on LSE relationships  3.1.2 X-ray crystal structure analysis and powder reflectance UV/Vis  spectroscopy  3.1.2.1 Solid-state X-ray crystal structure analysis  3.1.2.2 UV/Vis diffuse reflectance spectra of the solid powders  3.1.3 Adsorption of aromatic amino ketones on Aerosil 300  3.1.4 Sol-gel materials containing aromatic amino ketones  3.1.4.1 Physical entrapment in a microporous silica network  3.1.4.2 Chemical linking to the silica network 3.2 N-(2’-hydroxy-4’-dimethylaminobenzylidene)-4-nitroaniline [HDBN]  3.2.1 UV/Vis absorption spectroscopy of HDBN  3.2.2 X-ray crystal structure analysis and powder reflectance UV/Vis  spectroscopy of HDBN  3.2.3 Adsorption of HDBN on Aerosil 300 3.3 Poly(benzophenone co-piperazine) and its silica-composite  3.3.1 Syntheses and structure analysis  3.3.2 Characterization

3 5 6 7 10 10 11 12 16 18 21 23 25 25

25 25 36

52 52 63 68 73 73 83 90 90

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96 99 102 102 110

Contents

IV V 5.1 5.2. 5.3 5.4 5.5 VI

 3.3.2.1 Electrokinetic data  3.3.2.2 Thermal stability  3.3.2.3 N 2 adsorption/desorption data 3.3.3 Solvatochromic analysis Summary Experimental section General considerations 5.1.1 Instruments 5.1.2 Working procedures 5.1.3 Correlation analysis 5.1.4 Starting materials Synthetic part 5.2.1 Aromatic amino ketones by Friedel Craft acylation reaction 5.2.2 Aromatic amino ketones by nucleophilic aromatic substitution reaction 5.2.3 3-(4-Di(2-hydroxyethyl)amino)phenyl-1-(2-furyl)-2-propene-1-one 5.2.4 N-(2’-hydroxy-4’-dimethylaminobenzylidene)-4-nitroaniline Preparation of sol-gel hybrid materials 5.3.1 Physical entrapment in a microporous silica network 5.3.2 Chemical linking to the silica network Poly(benzophenone co-piperazine) and its composite form 5.4.1. Solution polymerization 5.4.2. Solid-state polymerization Crystal structure analyses References

4

110 112 114 115 119 123 123 123 125 125 125 126 126 129 132 132 133 133 134 137 137 137 137 142

List of publications

List of publications

Original contributions:

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1.El-Sayed, M.; Müller, H.; Rheinwald, G.; Lang, H.; Spange, S.: Linear solvation energy (LSE) correlations of the solvatochromic response and x-ray structure analysis of hydrophilicallyN-substituted Michler’s Ketone Derivatives.J. Phys. Org. Chem.2001,14, 247-255. 2.Zimmermann, Y.; El-Sayed, M.; Prause, S.; Spange, S.: The Solvent-Like Nature of Silica Particles in Organic Solvents.Monatsh. Chem.2001,132, 1347-1361. 3.Spange, S.; El-Sayed, M.; Müller, H.; Rheinwald, G.; Lang, H.; Poppitz, W.: Solid-state Structures of N-substituted Michler’s Ketones and their relation to Solvatochromism.Eur. J. Org. Chem.2002,24, 4159-4168. 4.El-Sayed, M.; Müller, H.; Rheinwald, G.; Lang, H.; Spange, S.: UV/Vis spectroscopic properties of N-(2’-hydroxy-4’-N,N-dimethyl-aminobenzylidene)- 4-nitroaniline in various solvents and solid environments.Monatsh. Chem.2003, 134, 361-370. 5.El-Sayed, M.; Müller, H.; Rheinwald, G.; Lang, H.; Spange, S.: Solvatochromism, Crystallochromism, and Solid State Structures of Hydrophilically Functionalized Aromatic Amino Ketones containing Furan and Thiophene Rings.Chem. Mat.2003,15, 746-754. Poster: 1.El-Sayed, M.; Schmidt, C.; Spange, S.; Kricheldorf, H.: Hydrophilically Functionalized Michler’s Ketone Derivatives as Polarity Probes for Different solid Materials. Berliner Polymerntage 2000, Poster (P 64, page 127), Berlin, 9. - 11. October2000.

Acknowledgement

Acknowledgement

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 The experimental part of this work was carried out in the laboratories of Prof. Dr. Stefan Spange, Chemnitz University of Technology from July 1998 until April 2002.  First of all, I wish to express my deep thanks and gratitude to Prof. Dr. Stefan Spange, who welcomed me in his research group, who introduced me into German life and who suggested the point and successfully guided me through my studies. I would like to thank Prof. Dr. Heinrich Lang very much for his scientific support in crystal structure analyses, and his evaluation of this thesis. I would also like to thank Dr. Gerd Rheinwald for X-ray intensity data collection. My deepest thanks are also to Dr. Hardy Müller for his interest and continuous encouragement. I would like to thank staff members in our research group for their co-operation, friendship by means which the daily work has always been a pleasure. I want to express my deepest gratitude to my parents Kauther El-Gamel and Mohamed El- Sayed, and to my sister Frial and to my brothers Ashraf and Ibrahim for their constant support and understanding. I extend my thanks to my wife Dr. Eng. Hanan Koutta and my daughters Mirna and Manar for understanding my demanding work and long working hours. Finally, I would like to thank the Germany Ministry of Education, the Fonds der Chemischen Industrie, Frankfurt am Main and Chemnitz University of Technology for their financial support.

Symbols and abbreviations

Symbols and abbreviations

δ

β α δ π* 2 δ H δ H λ max ν max + [M ] a a.u. b

b.p. BBP BET BuOH CH CP d D DAFP DCE DCM dd DEE DEI DeOH DH DMAc DMF DMSO DPAB

chemical shift

hydrogen-bond accepting capacity

hydrogen-bond donating capacity

polarizability correction term

dipolarity/polarizability

solvent cohesive energy density

hildebrand solubility parameter

maximum wave length

maximum wave number

molecule-ion

solvent-independent correlation coefficient ofα

arbitrary units

Solvent-independent correlation coefficient ofβ

boiling point 1,4-bis(4-benzoylphenyl)piperazine brunauer-Emmett-Teller 1-butanol c-hexane cross-polarization doublet

two oxygen atoms and two alkyl group attached to silicon atom 3-(4-di(2-hydroxyethyl)amino)phenyl-1-(2-furyl)-2-propene-1-one 1,2-dichloroethane dichloromethane doublet of doublets diethyl ether desorption electron ionization 1-decanol Dollimore-Heal N,N-dimethylacetamide

N,N-dimethylformamide dimethylsulfoxide 4-dimethylamino-4’-[di(2-propyltriethoxysilylcarbamatoethyl)amino]- benzophenone

7

Symbols and abbreviations

DPAF DPAT DSC EG ESI EtOH Exp. Sect. F Fig. FT-IR Fur(OAc) 2 Fur(OH) 2 g h HBA HBD HDBN HeOH HFP J LSE m.p. m/z MALDI-TOF MAS MeOH MHz MK MK(mor) 2 MK(NEt 2 ) 2 MK(OAc) 2 MK(OH) 2 MK(pip) 2 MK(pipaz) 2 MK(pipazOH) 2 MK(pipOEt) 2 mmol

[4-di(2-propyltriethoxysilylcarbamatoethyl)amino]-2-furylmethanone [4-di(2-propyltriethoxysilylcarbamatoethyl)amino]-2-thienylmethanone differential scanning calorimetry ethane-1,2-diol electron spray ionization ethanol experimental section significance figure Fourier transform-Infrared [4-di(2-acetoxyethyl)aminophenyl]-2-furylmethanone [4-di(2-hydroxyethyl)aminophenyl]-2-furylmethanone gram hour hydrogen-bond accepting hydrogen-bond donating N-(2’-hydroxy-4’-dimethylaminobenzylidene)-4-nitroaniline 1-hexanol 1,1,1,3,3,3-hexafluoro-2-propanol coupling constant linear solvation energy melting point mass/charge

matrix assisted laser desorption ionization time-of-flight magic angle spinning methanol megahertz 4,4’-bis-(dimethylamino)benzophenone, Michler’s Ketone 4,4’-bis(morpholino)benzophenone 4,4’-bis(diethylamino)benzophenone 4-dimethylamino-4’-[di(2-acetoxyethyl)amino]benzophenone 4-dimethylamino-4’-[di(2-hydroxyethyl)amino]benzophenone 4,4’-bis(piperidino)benzophenone 4,4’-bis(piperazino)benzophenone 4,4’-bis[4-(2-hydroxyethyl)piperazino]benzophenone 4,4’-bis(4-ethoxycarbonylpiperazino)benzophenone millimole

8

Symbols and abbreviations

MS MTMOS N n nm NMR OcOH Ormosil pm PrOH PSD Q r s SD T t Tab. TCE TEOS TFE T g TGA Thi(OAc) 2 Thi(OH) 2 TMOS tol. UV/Vis

mass spectra

methyltrimethoxysilane normal number of solvents nano-meter nuclear magnetic resonance 1-octanol organically modified silica pico-meter 1-propanol pore-size distribution four oxygen atoms attached to silicon atom correlation coefficient solvent-independent correlation coefficient ofπ*

standard deviation three oxygen atoms and one alkyl group attached to silicon atom triplet table 1,1,2,2-tetrachloroethane tetraethylorthosilicate 2,2,2-trifluoroethanol glass transition temperature

thermogravimetric analysis

[4-di(2-acetoxyethyl)aminophenyl]-2-thienylmethanone [4-di(2-hydroxyethyl)aminophenyl]-2-thienylmethanone tetramethoxysilane toluene ultraviolet/visible

9

General part

I.

General part

10

1.1 Introduction  The color change of a compound induced by external influences, e. g. by solvents (solvatochromism), applied stress (mechanochromism), salts (halochromisms) and/or 1-9 temperature (thermochromism) has been studied intensively over the last decades. In this context, solvatochromic dyes have been established as empirical polarity indicators for 1,10-13 solvents, solvent mixtures and solution of several solutes in various liquids. This empirically derived concept for volume effects has been also widespread applied to evaluate 14-24 the internal and external polarities of surfaces of macro-molecular and related materials. In this sense, the term surface polarity is an argument often used in interpreting experimental 22 25 results obtained from Chromatography and heterogeneous catalysis. The effect of solid matrix is important, because many compounds (such as dyes, stabilizers and others) are applied as components of a more complex system in the solid phase. Therefore it is important to evaluate the medium effect for these systems as well.  The solvatochromic effects of rigid matrices are complex and as yet less understood as compared with solvents. It is important to take into account not only the matrix itself but its mode of preparation and the way in which the solute has been incorporated into the matrix. To date, no generally agreed upon definition of the term surface polarity has emerged. In the broadest and most general sense the surface polarity can be viewed as the sum of all interactive forces between an adsorbed molecule and the occupied surface site or sites. This 1,26 definition is based on the related interpretation of the term solvent polarity. Most solvent polarity scales are empirical and are based on kinetic, thermodynamic, or spectroscopic data 1 relating to certain reference reactions. Significantly, different empirical solvent polarity scales have been shown to correlate well with each other, pointing to the existence of an 1 underlying common feature.  Since, a chromophor is covalently functionalized by a polar group or another suitable moiety for molecular recognition in its periphery, manifold influences on the UV/Vis spectra can result from the intermolecular interaction in the solid-state (crystal) or in molecular 27-31 aggregates of the dye. Thus, quantum size effects have been observed for organic nano- 29 28 crystals and carotenoid dye nano-particles. However, two different influences, the supra- molecular structure and quantity of accumulated dye molecules in the nanocrystal seem of importance for the resulting UV/Vis spectroscopic property. Because both influences are

General part

11

associated properties, a reasonable interpretation of the UV/Vis spectrum of those nanosized dye aggregates is still complicated and requires further experimental results and theoretical studies.  Examination of chromophoric aggregates and supramolecular structures by UV/Vis spectroscopy is an experimental challenge and of importance both for academic research and 28-31 for practical applications in nano-science. For this objective, the exact knowledge of solid-state structures (X-ray structure analysis) is necessary and the corresponding UV/Vis spectra have to be significantly different as function of structure variation. This requires the choice of suitable model systems which show color changes as function of nature of accumulation processes. 1.2 Solvatochromism  Solvatochromism is defined as the pronounced change in position and sometimes intensity of an electronic absorption or emission band accompanying a change in the polarity 1 of the medium. This medium may include solids, micelles, organized molecular films and 1c even a vacuum, apart from liquid solvents. Solvatochromic shifts result from the difference of solvation energies between the two electronic states involved in the observable absorption or emission transition. These shifts are important for the description of the relative energies of

electronic states, the dipole moment and polarizability of molecules. In addition they often provide information about specific interactions such as hydrogen bonding.  Quantification of general properties of solvents and micelle environments has been 1 studied by physical organic chemists for many years. Using solvatochromic probe dyes has several advantages: the measurements require very low concentrations of the probe molecules, are easy to do, and reproduce well. The requirement is that the employed probe dye must adequately reflect the relevant properties of the environment under study. The responses of solvatochromic indicators on changing solvent environments have been used as 1b the phenomenological basis for several empirical „solvent polarity“ scales. Among such 1,32 quantitative scales, the Kamlet-Taft system is the most inclusive with respect to all solvent types and it is well supported by theoretical reaction field models for the solvent influences 32,33 upon the solvatochromic probes.  The general equation for the influence of solvent effects on a single solute is shown as 1,10,32 eq 1, where XYZ is the property to be correlated 2 XYZ = (XYZ) 0 + hδ H + s(π* + dδ) + aα+ bβ (1)