Piperidine (eBook)

Front Cover 1
Piperidine: Structure, Preparation, Reactivity, and Synthetic Applications of Piperidine and its Derivatives 4
Copyright Page 5
Table of Contents 10
Preface 8
Chapter 1. PIPERIDINE. A GENERAL SURVEY 18
1.1. SYNTHETIC ASPECTS 20
1.2. PIPERIDINE AS A SOLVENT 27
1.3. PIPERIDINE AS A BASE AND AS A NUCLEOPHILE 27
1.4. REACTIVITY OF PIPERIDINE. A PREVIEW 31
1.5. REFERENCES 37
Chapter 2. CONFORMATIONAL ANALYSIS OF PIPERIDINE 41
2.1. THE CHEMICAL SHIFT DIFFERENCE (dae) METHOD 43
2.2. CONTROVERSY AND THE PRESENT SITUATION 45
2.3. REFERENCES AND NOTES 49
Chapter 3.1H NMR PROPERTIES OF PIPERIDINE DERIVATIVES 51
3.1. INTRODUCTION 52
3.2.1H NMR OF PIPERIDINE AND METHYLPIPERIDINES 52
3.3. 2-ARYL-4-PIPERIDONES 77
3.4. ARYLPIPERIDINES 80
3.5. APPLICATION OF TWO-DIMENSIONAL NMR TECHNIQUES TO PIPERIDINE DERIVATIVES 86
3.6. REFERENCES 101
Chapter 4.13C NMR SPECTROSCOPY OF PIPERIDINE DERIVATIVES 105
4.1. NITROGEN INVERSION IN PIPERIDINE AND N-METHYL PI PERI DINE 106
4.2. C-ALKYLPIPERIDINES 107
4.3. N-INVERSION IN HINDERED PIPERIDINES 110
4.4. METHYL SUBSTITUTED PIPERIDINIUM SALTS 111
4.5. CONFORMATIONAL EQUILIBRIA IN QUATERNARY PIPERIDINIUM SALTS 114
4.6. 4-PHENYLPIPERIDINES AND 4-PHENYL-4-PIPERIDINOLS 116
4.7. 3-ARYLPI PERI DINES 126
4.8. PIPERIDONES AND 2-ARYL-4-PIPERIDONES 128
4.9. PIPERIDINES WITH FUSED RINGS 133
4.10. AZABICYCLO[3.3.1]NONANE DERIVATIVES 141
4.11. REFERENCES 148
Chapter 5. MASS SPECTROMETRY OF PIPERIDINE DERIVATIVES 152
5.1. SIMPLE PIPERIDINE COMPOUNDS:PIPERIDINE N-METHYLPIPERIDINE AND PIPERIDINE ALKALOIDS 153
5.2. PIPERIDONES AND 4,4-ETHYLENEDIOXYPIPERIDINES 163
5.3. PIPERIDINOLS AND 4-AMINOPIPERIDINES 170
5.4. N-ACYLPIPERIDINES 174
5.5. PIPERIDINE N-OXIDES 175
5.6. BICYCLIC PIPERIDINE COMPOUNDS 176
5.7. STRUCTURAL ELUCIDATION OF ALKALOIDS 185
5.8. REFERENCES 186
Chapter 6. 2-ARYLPIPERIDINES AS SUITABLE MODELS FOR STUDYING ROTATIONAL BARRIERS AROUND Csp2- Csp3 BONDS 189
6.1. INTRODUCTION 190
6.2. 3-ARYLPIPERIDINOLS: DENDROCREPINE ALKALOID 190
6.3. 2-ARYL-4-PIPERIDONES 191
6.4. REFERENCES 209
Chapter 7. N-ACYLPIPERIDINES. A USEFUL TOOL FOR STEREOCONTROL IN ORGANIC SYNTHESIS 210
7.1. STUDY OF ROTATIONAL EQUILIBRIUM AROUND THE AMIDE BOND IN N-ACYLPIPERIDINES BY1H NMR SPECTROMETRY 211
7.2. STRUCTURAL ELUCIDATION OF N-ACYLPIPERIDINES BY 13C NMR DETERMINATION OF AMIDE ROTATIONAL BARRIERS 227
7.3. N-ACYLPIPERIDINES AS A USEFUL TOOL FOR STEREOCONTROL IN ORGANIC SYNTHESIS 236
7.4. REFERENCES 240
Chapter 8. STRUCTURE AND SYNTHETIC APPLICATIONS OF a-CYANOTETRAHYDROPYRIDINES AND a-CYANOPIPERIDINES 242
8.1. SYNTHESIS AND SYNTHETIC APPLICATIONS OF 2-CYANO-1,2,3,6-TETRAHYDROPYRIDINES 243
8.2. SYNTHESIS AND SYNTHETIC APPLICATIONS OF 2-CYANO-1,2,5,6-TETRAHYDROPYRIDINES 252
8.3. SYNTHESIS AND SYNTHETIC APPLICATIONS OF 2-CYANOPIPERIDINES 264
8.4. SYNTHESIS AND SYNTHETIC APPLICATIONS OF 2-CYANO-6-OXAZOLOPIPERIDINES 289
8.5. EXOCYCLIC a-CYANOPIPERIDINES 299
8.6. STEREOCHEMICAL ASPECTS OF 2-CYANOPIPERIDINES AND 2-CYANOTETRAHYDROPYRIDINES 307
8.7. Í MR SPECTROSCOPY OF 2-CYANOPIPERIDINES AND 2-CYANOTETRAHYDROPYRIDINES 314
8.8. REFERENCES 325
Chapter 9. PIPERIDONES AS USEFUL INTERMEDIATES IN ORGANIC SYNTHESIS 330
9.1. SYNTHESIS OF PIPERIDONES 331
9.2. SYNTHESIS OF ARYLPIPERIDONES 370
9.3. SYNTHETIC APPLICATIONS OF PIPERIDONES 390
9.4. REFERENCES 438
10. SUBJECT INDEX 452