Ph. D. THESIS 2009

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JURY “BABES-BOLYAI” UNIVERSITY CLUJ-NAPOCA FACULTY OF CHEMISTRY AND CHEMICAL ENGINEERING ORGANIC CHEMISTRY DEPARTMENT Ph. D. THESIS Contributions to the Synthesis and Structural Analysis of Some Bicyclic Compounds and to the Fabrication of 3D Metallic Micro – and nanostructures by Laser Induced Photochemistry Ph.D. Thesis Abstract Ph. D. Student Nicoleta Ioana TOŞA President Prof. Dr. Ioan Silaghi-Dumitrescu, Dean of the Faculty of Chemistry and Chemical Engineering, Cluj-Napoca Scientific advisor Prof. Dr. Ion Grosu, Faculty of Chemistry and Chemical Engineering, Cluj-Napoca Reviewers Prof. Dr. Ionel Mangalagiu, University “Al.I. Cuza”, Iasi D. R. Dr. Patrice Baldeck, University “Joseph Fourier”, Grenoble, France Prof. Dr. Simion Astilean, University “Babes- Bolyai”, Cluj-Napoca Defense on 7 th October 2009 1
General Introduction OUTLINE Part A Synthesis and Structural Analysis of Some Bicyclo[3.3.1]nonane Derivatives 1. Bicyclo[3.3.1]nonane-3,7-dione 11 1.1. Introduction 11 1.1.2. Synthesis of bicyclo[3.3.1]nonane-3,7-dione 11 1.3. Structural aspects in solution 13 1.3.1. NMR investigations 13 1.3.1.1. Tetramethyl 3, 7-dihydroxybicyclo[3.3.1] nona-2, 6-diene -2, 4, 6, 8-tetracarboxylate 13 1.3.1.1. Bicyclo[3.3.1]nonane-3,7-dione 17 1.3.2. FT-IR investigation of tetramethyl 3, 7-dihydroxybicyclo[3.3.1] nona- 2, 6-diene-2, 4, 6, 8-tetracarboxylate 20 1.4. Solid state investigations 23 1.4.1. FT-IR and Raman investigations 23 1.4.1.1. Tetramethyl 3, 7-dihydroxybicyclo[3.3.1] nona-2, 6-diene- 2,4,6,8-tetracarboxylate 24 1.4.1.2. Bicyclo[3.3.1]nonane-3,7-dione 30 1.4.2. Mass spectrometry study of bicyclo[3.3.1]nonane-3,7-dione 35 1.4.3. Single crystal X-ray diffraction investigations 38 1.4.3.1. Tetramethyl 3,7-dihydroxybicyclo [3.3.1] nona-2,6- diene-2,4,6,8-tetracarboxylate 38 1.4.3.2. Bicyclo[3.3.1]nonane-3,7-dione 40 1.5. Molecular modeling: structure and IR spectra 42 1.5.1. Tetramethyl 3,7-dihydroxybicyclo[3.3.1]nona-2,6-diene- 2,4,6,8-tetracarboxylate structure 42 1.5.2. Bicyclo[3.3.1]nonane-3,7-dione 48 1.6. Attempts of synthesis of spiro-bis(dioxane) bicyclic compounds type 50 1.6.1. Synthesis of spiro-monodioxane compounds 50 1.6.2. NMR spectra in solution 51 1.6.3. Mass spectra of monospirane 56 1.6.4. FT-IR measurements 60 2. Bicyclo[3.3.1]nonane-3,7-dione dioxime 62 2.1. Introduction 62 2.2. Synthesis of syn and anti isomers 63 2.3. Investigations in solution 66 2.3.1. NMR spectra of syn and anti isomers 66 2.3.2. NMR study of kinetics of the synanti isomerisation 70 2.3.3. Chiral HPLC studies 74 2.3.3.1. Investigation of a mixture of syn and anti isomers 74 2.3.3.2. Investigation of the isolated anti isomer 76 2.3.4. FT-IR study 77 2.4. Investigation of bicyclo[3.3.1]nonane-3,7-dione dioxime in solid state 80 2.4.1. FT-IR 80 2.4.2. Single crystal X-ray diffraction 83 2
Page 1: “BABES-BOLYAI” UNIVERSITY CLUJ-
Page 5 and 6: 3.6.1. Dots 188 3.6.2. 3D structure
Page 7 and 8: Part A: Synthesis and Structural An
Page 9 and 10: H 3C H 3C O O O C C O O 1a O O C C
Page 11 and 12: The two forms are in equilibrium an
Page 13 and 14: Figu re 4 . Th e 13 C-NMR APT (CDCl
Page 15 and 16: set used , the anarmonicities that
Page 17 and 18: Figure 9. ORTEP diagram for the bic
Page 19 and 20: 1.5.1. Tetramethyl 3,7-dihydroxybic
Page 21 and 22: Table 7. The selected molecular par
Page 23 and 24: a b Figure 14. 1 H NMR spectrum (CD
Page 25 and 26: Figure 16. 13 C NMR spectrum APT (C
Page 27 and 28: Absorbance (a. u.) Absorbance (a.u.
Page 29 and 30: icyclo[3.3.1]nonane-3,7-dione solut
Page 31 and 32: m u lt ip let a t a t δ ==1 .7 6 p
Page 33 and 34: Figure 22. 13 C NMR APT spectrum of
Page 35 and 36: Figure 24. NMR investigation of the
Page 37 and 38: (mol·l -1 ) syn 8.8 x10 -3 1.4373
Page 39 and 40: a b Figure 29. 3D FTIR spectra in s
Page 41 and 42: Figure 32. ORTEP diagram for the cy
Page 43 and 44: H2 … N3 = 1.839 Å H5 … N6 = 1.
Page 45 and 46: 2. Conclusions of the part A Differ
Page 47: 20. L. J. Bellamy, “Advanced in I
Page 50 and 51: 2. Experimental part: fabrication a
Page 52 and 53:
3 m 30 m a b Figure 4. Optical imag
Page 54 and 55:
(NA 1.25) in phase-contrast (a) and
Page 56 and 57:
was chosen instead of an aqueous on
Page 58 and 59:
Our goal is to develope a lasser as
Page 60 and 61:
Figure 15. a Optical image of gold
Page 62 and 63:
the power as parameter exhibits a m
Page 64 and 65:
a b Figure 21 a) Optical image of g
Page 66:
4.5.3. 3D structures The 3D structu
Page 69 and 70:
Selected References 1. E. S. Wu, J.
Page 71:
VIII. J. Bosson-Ehoomann, A. Mihut,
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Ph. D. THESIS 2009

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