Advances in heterocyclic chemistry. Volume 128 /

Advances in Heterocyclic Chemistry, Volume 128, is the definitive series in the field--one of great importance to organic chemists, polymer chemists and many biological scientists. Because biology and organic chemistry increasingly intersect, the associated nomenclature is being used more frequently...

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Bibliographic Details
Corporate Author:	ScienceDirect (Online service)
Other Authors:	Scriven, Eric F. V. (Editor), Ramsden, Christopher A., 1946- (Editor)
Format:	eBook
Language:	English
Published:	Amsterdam : Academic Press, 2019.
Subjects:	Heterocyclic chemistry. Heterocyclic compounds. Chimie des composés hétérocycliques. Composés hétérocycliques. Heterocyclic chemistry Heterocyclic compounds Electronic books.
Online Access:	Connect to the full text of this electronic book

Table of Contents:

Front Cover
Advances in Heterocyclic Chemistry
Copyright
Contents
Contributors
Preface
Chapter One: Recent advances in 1,2,4-triazolo[1,5-a]pyrimidine chemistry
1. Introduction
1.1. General survey
1.2. Scope and limitation
1.3. Nomenclature
2. Occurrence and synthesis
2.1. Survey
2.2. Occurrence
2.3. Syntheses from 5-amino-1,2,4-triazoles and 1,3-biselectrophiles
2.3.1. Principle and conditions
2.3.2. The diversity of biselectrophiles
2.3.3. Regioselectivity
2.3.4. The direct synthesis of triazolopyrimidines substituted onto carbon ring atoms
2.3.5. The use of modified biselectrophiles
2.3.6. The use of polyfunctional electrophiles
2.3.7. Syntheses via dihydro triazolopyrimidines
2.3.8. Multicomponent reactions
2.3.9. Special syntheses
2.4. Syntheses using special aminotriazole derivatives
2.4.1. Syntheses of N-substituted triazolopyrimidines
2.4.2. The use of aminotriazole-based intermediates
2.5. Triazole ring syntheses
2.5.1. Syntheses from 1,2-diaminopyrimidines
2.5.2. Syntheses from N-(pyrimid-2-yl)amidine-series compounds
2.5.3. Syntheses from 2-hydrazinopyrimidines
2.5.4. Other triazole ring syntheses
2.6. Other routes to triazolopyrimidines
2.6.1. Aromatization of dihydro derivatives
2.6.2. Ring transformation and cleavage
3. Structure
3.1. Theoretical methods
3.2. X-ray diffraction
3.3. Molecular spectra
3.3.1. H NMR spectra
3.3.2. C NMR spectra
3.3.3. F NMR spectra
3.3.4. Electronic spectra
3.3.5. Infrared and Raman spectra
3.3.6. Mass spectra
3.4. Physicochemical properties
3.5. Tautomerism
4. Reactivity
4.1. Triazolopyrimidines as bases and acids
4.1.1. Protonation and dissociation
4.1.2. Coordination
4.2. Alkylation at nitrogen ring atoms
4.3. Carbon-carbon coupling at ring atoms.
4.3.1. The use of organometallic and metal salt reagents
4.3.2. Suzuki coupling
4.3.3. Sonogashira coupling
4.3.4. Oxidative coupling
4.3.5. Reductive coupling
4.3.6. Nucleophilic addition
4.4. Other reactions at ring atoms
4.5. Nucleophilic substitution of functional groups at the rings
4.5.1. Substitution of halogen
4.5.2. Substitution of oxygen-, sulfur-, or nitrogen-containing functions
4.6. Transformation of individual substituents
4.6.1. Oxygen- or sulfur-containing groups
4.6.2. Amines and their derivatives
4.6.3. Carbonyl containing groups
4.7. Ring cleavage and recyclization
4.8. Anellation of heterocyclic rings
4.8.1. Anellation onto 6/7 positions
4.8.2. Anellation onto other positions
4.9. Reactivity of side chains
4.9.1. Reactions involving halogen or oxygen functionalities
4.9.2. Reactions involving sulfur, nitrogen, or phosphorus functionalities
4.9.3. Formation of hydrocarbon groups
4.9.4. Formation of diheterocyclyl compounds
5. Application
5.1. Pharmaceutical use
5.2. Agrochemical use
5.3. Optical and information recording uses
5.4. Other uses
References
Chapter Two: Fluorescent heterocycles: Recent trends and new developments
1. Introduction
2. Furans and benzofurans: Sustainable fluorophores
3. Si-rhodamines: Xanthenes and silicon united
4. 4H-imidazoles: Brightness and darkness combined
5. Imidazolinones: The chromophore of the GFP
6. Thiazoles: Learning from firefly
7. Oxazoles and benzoxazoles: More than scintillators and optical brighteners
8. Oxadiazoles and benzoxadiazoles: From antiretroviral drugs to omni functional fluorophores
9. Quinolizinium salts: Water-soluble isoelectronic analogous of anthracene
10. Acridines and acridones: Beyond acridine orange.
11. Triazines: Toward fluorescent covalent organic frameworks
12. Tetrazines: Fluorescent biorthogonal labeling
13. Imidazopyridines: Efficient ESIPT dyes
14. Imidazoquinoxalines: High quantum yields for blue OLEDs
15. Azaacenes: High-tech materials for organic electronics
16. Concluding remarks
Acknowledgments
References
Chapter Three: Recent developments in the synthesis of the BODIPY dyes
1. Introduction
2. Synthesis of the BODIPY core
2.1. Synthesis of symmetrical BODIPYs
2.1.1. From pyrroles and acid anhydrides
2.1.2. From pyrroles and acid chlorides
2.1.3. From pyrroles and orthoesters
2.1.4. From pyrroles and thiophosgenes
2.1.5. From pyrroles and aldehydes, with subsequent oxidation
2.2. Synthesis of unsymmetrical BODIPYs
2.2.1. From pyrroles and 2-ketopyrroles
2.3. Boron chelation of dipyrromethenes
3. Updates on classical modifications of the BODIPY core
3.1. Electrophilic aromatic substitutions
3.1.1. SEAr of BODIPYs, 2/6-substitution
3.1.2. SEAr of dipyrromethanes, 3/5-substitution
3.2. Nucleophilic aromatic substitutions
3.2.1. SNAr of BODIPYs, 3/5-substitution with O-centered nucleophiles
3.2.2. SNAr of BODIPYs, 3/5-substitution with N-centered nucleophiles
3.2.3. SNAr of BODIPYs, 3/5-substitution with C-centered nucleophiles
3.2.4. SNAr of BODIPYs, 3/5-substitution with chalcogen nucleophiles
3.2.5. SNAr of BODIPYs, 1,7-substitution
3.2.6. SNAr of BODIPYs, 8-substitution
3.3. Knoevenagel condensation of 3,5-dimethyl-substituted BODIPYs
3.4. Substitution at boron
3.4.1. Intermolecular substitution at boron, fluorine to carbon
3.4.2. Intramolecular substitution at boron, fluorine to oxygen
3.4.3. Intermolecular substitution at boron, fluorine to oxygen
3.4.4. Substitution at boron via BCl2-BODIPYs, fluorine to oxygen or nitrogen.
3.4.5. Reaction of dipyrromethenes with functionalized borons
3.5. Substitution of 8-thiomethyl groups
3.5.1. SNAr of 8-thiomethyl BODIPYs
3.5.2. Liebeskind-Srogl cross-coupling of 8-thiomethyl BODIPYs
3.5.3. Reduction of 8-thiomethyl BODIPYs
3.6. Palladium-catalyzed cross-coupling reactions of BODIPYs
3.6.1. Cross-coupling reactions of haloBODIPYs
3.6.2. Regioselectivity of palladium-catalyzed cross-couplings
3.6.3. Negishi cross-couplings reactions of haloBODIPYs
3.6.4. Cascade cross-coupling reactions, Suzuki-Miyaura-Knoevenagel
3.6.5. Palladium-catalyzed silylation of BODIPYs
3.6.6. Miyaura borylation of BODIPYs
4. New methods for modification of the BODIPY core
4.1. Transition metal-catalyzed direct CH functionalization
4.1.1. Direct CH functionalization of BODIPYs, 3/5-functionalization
4.1.2. Direct CH functionalization of BODIPYs, 2/6-functionalization
4.1.3. Miyaura-Ishiyama-Hartwig borylation of dipyrromethenes and BODIPYs
4.1.4. Direct CH functionalization/annulation of BODIPYs
4.1.5. Direct C(sp)H arylation of 8-methyl BODIPYs
4.2. Oxidative nucleophilic substitution of hydrogen
4.3. Vicarious nucleophilic substitution
4.4. Radical-mediated functionalization
4.4.1. Radical-mediated 3/5-alkylation
4.4.2. Radical-mediated 3,5-diamination
4.5. Oxidative dimerization
4.6. Aldol-like reactions of 8-methyl BODIPYs, functionalization at 8-methyl
4.7. Nucleophilic substitution of 8-chloromethyl BODIPYs, functionalization at 3/5-methyl
5. Conclusions
References
Chapter Four: Liquid crystalline derivatives of heterocyclic radicals
1. Introduction
2. Liquid crystalline derivatives of cyclic aminoxyl radicals
2.1. Derivatives of the 4,4-dimethyl-3-oxazolidinyloxyl (DOXYL) radical (A)
2.1.1. Molecular design vs liquid crystalline behavior.
2.1.2. Magnetic properties
2.2. Derivatives of the 2,2,6,6-tetramethyl-1-piperidynoxyl (TEMPO) radical (B)
2.2.1. Molecular design and synthesis of liquid crystalline derivatives
2.2.1.1. Rod-like mesogens
2.2.1.2. Bent-core mesogens
2.2.1.3. Dimesogens
2.2.1.4. Disc-shaped mesogens
2.2.1.5. Polymers
2.2.2. Magnetic properties
2.3. Derivatives of the 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (NIT) radical(C)
2.4. Derivatives of the 1-pyrrolidinyloxyl (PROXYL) radical (D)
2.4.1. Rod-like derivatives
2.4.1.1. Synthesis
2.4.1.2. Liquid crystalline behavior
2.4.2. Derivatives forming columnar phases
2.4.3. Magnetic properties
3. Liquid crystalline derivatives of the 6-oxoverdazyl (E) and 6-thioxoverdazyl radicals
3.1. 6-Oxoverdazyl and 6-thioxoverdazyl: Chemistry and properties
3.2. Liquid crystalline derivatives
3.2.1. Disc-shaped derivatives of the 6-oxoverdazyl
3.2.2. Bent-core and hockey-stick derivatives of 6-oxoverdazyl and 6-thioxoverdazyl
3.2.3. Extended half-disc derivatives of the 6-oxoverdazyl
3.2.4. Bent-core diradical derivatives of the 6-oxoverdazyl
3.3. Other properties of liquid crystalline derivatives of 6-oxoverdazyl
3.3.1. Magnetic properties
3.3.2. Electronic absorption spectroscopy
3.3.3. Semiconductive properties
4. Liquid crystalline derivatives of the 1,4-dihydrobenzo[e][1,2,4]triazin-4-yl radical (F and G)
4.1. Fundamental properties of the benzo[e][1,2,4]triazin-4-yl
4.2. Synthesis of benzo[e][1,2,4]triazin-4-yl derivatives
4.3. Liquid crystalline derivatives
4.3.1. Disc-like derivatives
4.3.2. Bent-core derivatives
4.4. Other properties of liquid crystalline derivatives of benzo[e][1,2,4]triazin-4-yl
4.4.1. Magnetic properties
4.4.2. Electronic absorption spectroscopy
4.4.3. Semiconductive properties.