Ph. D. THESIS 2009

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
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