Nitro Compounds: Recent Advances in Synthesis and Chemistry

This multi-authored work reviews and evaluates the growing importance of the nitro group function. It describes the powerful influence of the nitro group on recent progress in organic synthesis and emphasizes recent developments in the chemistry of this group. The contributors consider the increasingly significant role of organic nitro chemistry in providing a source of new reagents and in offering selective transformations. They provide a detailed review of nitrogen pentoxide chemistry which stresses its usefulness as a nitrating agent for various classes of organic compounds. Researchers, students and teachers will benefit from the combined knowledge and expertise of the authors. The editor has worked and taught in many countries. He has published extensively on organic nitrogen compounds and has discovered new methods. Special feature: Contains the first complete survey of aliphatic fluoronitro chemistry.

Table of Contents:
Series Forward; Preface; Chapter 1. The Nitro Function as a Leaving Group in Organic Synthesis; Noboru Ono; I. Replacement of Aliphatic Nitro Groups by Hydrogen; 1.1 Introduction; 1.2 Denitrohydrogenation; 1.3 Synthetic Applications; 1.3.1 Conjugate Addition of Alkyl Groups; 1.3.2 Synthesis of Ketones; 1.3.3 Synthesis of Alcohol Derivatives; 1.3.4 Regioselective Diels - Alder Reactions; 1.3.5 Synthesis of Deuterated Compounds; 1.3.6 Miscellaneous Applications; II. Replacement of Aliphatic Nitro Groups by Carbon and Heteroatoms; 2.1 Introduction; 2.2 Nucleophilic Substitution Reactions of Allylic Nitro Compounds; 2.3 Nucleophilic Substitution of Nitro Compounds via Electron Transfer Processes; 2.4 Lewis Acid Catalyzed Nucleophilic Substitution Reactions of Nitro Compounds; 2.5 Intramolecular Substitution Reaction of Aliphatic Nitro Compounds; 2.5.1 Formation of Cyclopropanes; 2.5.2 Formation of Furans; III. Alkene Forming Reactions Involving Elimination of One or Two Nitro Groups; 3.1 Introduction; 3.2 beta--Elimination Reactions of Nitrous Acid; 3.2.1 Conjugate Addition of Nucleophiles to Nitroalkanes and Elimination of Nitrous Acid; 3.2.2 Michael--Type Addition of Nitro Compounds Followed by Elimination of Nitrous Acid; 3.2.3 Hydroxyalkylation of Nitro Compounds and Elimination of Nitrous Acid; 3.2.4 Diels - Alder Reactions of Nitroalkenes and Elimination of Nitrous Acid; 3.2.5 Free--Radical Chain Substitution of Nitro Compounds Followed by Elimination of Nitrous Acid; 3.3 Radical Elimination of the Nitro Group; 3.3.1 Elimination from Vicinal Dinitro Compounds; 3.3.2 Elimination from beta--Nitrosulfones; 3.3.3 Elimination from beta--Nitrosulfides; IV. Concluding Remarks; References; Chapter 2. The Role of the Nitro Group in Carbohydrate Chemistry; Peter A. Wade; Robert M. Giuliano; I. Introduction; II. Structural Considerations for Nitro Sugars; 2.1 Characteristic Spectra; 2.2 Conformational Analysis; 2.3 Epimerization; 2.4 Tautomerization; 2.5 Summary of Structural Considerations; III. The Synthesis of Saturated Nitro Sugars and Related Materials; 3.1 Nitroaldol Approaches to Nitro Sugars and Related Compounds; 3.1.1 Recent Developments in the Nitroaldol Reaction; 3.1.2 Stepwise Construction from Simple Acyclic Precursors: Application to the Synthesis of 3--Nitro and 3--Amino Sugars; 3.1.3 Oxidative Cleavage of Sugars Followed by Double--Nitroaldol Condensation with Nitromethane; 3.1.4 Intramolecular Condensation of Sugar--Derived Nitroaldehydes; 3.1.5 Condensation of Sugars with Simple Nitro Compounds; 3.1.6 Condensation of Nitro Sugars with Aldehydes; 3.2 Oxidative Approaches to Nitro Sugars; 3.2.1 Preparation of 1--Nitro Sugars; 3.2.2 Preparation of 3--Nitro Sugars; 3.2.3 Ozonolysis of Phosphine Imines; 3.3 Nitro Sugar Synthesis via Alkyl Iodide--Nitrite Displacement; 3.4 Summary of Synthetic Approaches to Saturated Nitro Sugars; IV. Synthesis of Nitroalkenyl Sugars; V. Reactions of Nitroalkenyl Sugars; 5.1 Conjugate Addition; 5.2 1,3--Dipolar Cycloaddition; 5.3 Epoxidation; 5.4 Reaction with Sulfur Ylides; 5.5 Reduction; 5.6 Summary of Reactions of Nitroalkenyl Sugars; VI. Reactions of Nitro Sugars; 6.1 Conjugate Addition Reactions of Sugar Nitronates; 6.2 Nitroaldol Reactions of Saturated Nitro Sugars; 6.3 Substitution Reactions of Saturated Nitro Sugars; 6.4 Reduction of Saturated Nitro Sugars; 6.5 Conversion of the Nitro Group in Sugars to the Carbonyl Group; 6.6 Reactions of alpha--Nitroepoxides; 6.7 Summary of Reactions of Saturated Nitro Sugars; VII. Naturally Occurring Nitro Sugars; 7.1 Overview of Synthetic Routes; 7.2 Synthesis of Evernitrose; 7.3 Synthesis of Rubranitrose; 7.4 Synthesis of Kijanose; 7.5 Synthesis of Decilonitrose; 7.6 Summary of Synthetic Routes to the Naturally Occurring Nitro Sugars; VIII. New Developments; 8.1 Amino Sugar Synthesis Using Nitroisoxazolines; 8.2 Sugar Pyrazolines and Pyrazoles; 8.3 Nitroalditols; 8.4 Miscellaneous; Acknowledgment; References; Chapter 3. The Chemistry of Dinitrogen Pentoxide; John W. Fischer; I. Introduction; II. Preparations; III. Physical Properties; 3.1 Structure; 3.2 Spectra and Structure; 3.3 Photochemistry; 3.4 Thermal Decomposition in the Gas Phase; 3.5 Decomposition in Solution; IV. Reactions; 4.1 Aromatic Nitration Mechanism Studies; 4.2 Alternate Mechanisms for Aromatic Nitration in Solution; 4.3 Aromatic Nitration Kinetics of N 2 O 5 /HNO 3 ; 4.4 Aromatic Nitration Using N 2 O 5 with Lewis Acids; 4.5 Nitration of Naphthalene; 4.6 Nitration of Polycyclic Aromatic Hydrocarbons; 4.7 Reaction of Phenanthrene with N 2 O 5 ; 4.8 Reaction of N 2 O 5 with a Bridged Annulene; 4.9 Reaction of N 2 O 5 with Benzene and Substituted Benzenes; 4.10 Reaction of Alkanes with N 2 O 5 ; 4.11 Nitration of Perhydroanthracene; 4.12 Reaction of n--Octane with N 2 O 5 in HNO 3 ; 4.13 Photochemical Reaction of Adamantane with N 2 O 5 ; 4.14 Reactions of Alkenes with N 2 O 5 ; 4.15 Mechanism of N 2 O 5 Addition to Alkenes in Solution; 4.16 Salt Effect on the Addition of N 2 O 5 to Alkenes; 4.17 Stereochemistry of N 2 O 5 Addition to Alkenes; 4.18 Reaction of N 2 O 5 with Highly Substituted Alkenes; 4.19 Reaction of Stannyl--Substituted Acetylenes with N 2 O 5 ; V. O--Nitration; 5.1 Nitration of Aldehydes and Alcohols; 5.2 Nitration of Alcohols; 5.3 Nitration of Carbohydrates and Polyhydroxy Compounds with N 2 O 5 ; 5.4 Reaction of N 2 O 5 with Diethyl Ether; 5.5 Reaction of Alkyl Nitrites with N 2 O 5 ; 5.6 Acyl Nitrates; 5.7 Peroxy Nitrates; 5.8 Peroxyacid Nitrates; 5.9 Nitronium Trifluoromethanesulfonate; 5.10 Synthesis of Nitramines Using N 2 O 5 in Aprotic Solvents; 5.11 Preparation of Nitramines Using N 2 O 5 in HNO 3 ; 5.12 Nitramines from Amides and Imides and N 2 O 5 ; 5.13 Reaction of Carbodiimides with N 2 O 5 ; 5.14 Nitration of Sulfamide Salts; VI. Reaction of Strained--Ring Compounds with N 2 O 5 ; 6.1 Epoxides; 6.2 Aziridines; 6.3 Cyclopropanes; 6.4 Oxetanes; 6.5 Azetidines; VII. Reaction of N 2 O 5 with Unstrained--Ring Compounds; 7.1 Five--Membered Rings; 7.2 Six--Membered Rings; 7.3 Seven--Membered Rings; VIII. Reaction of N 2 O 5 with Strained--Ring Molecules Containing other Functionalities; IX. Reaction of Oximes with N 2 O 5 ; X. Conclusions; Acknowledgments; References; Chapter 4. Aliphatic Fluoronitro Compounds; Horst G. Adolph; William M. Koppes; I. Introduction; II. Synthesis of Fluoronitro Compounds; 2.1 Introduction of Fluorine; 2.1.1 Fluorination of Nitroalkyl Anions; 2.1.1.1 Fluorination of Mononitroanions; 2.1.1.2 Fluorination of 1,1--Dinitroanions; 2.1.2 Fluorination of Nitroalkyl - Metal Compounds; 2.1.3 Fluorination of Primary Nitramine Salts; 2.1.4 Fluorination of Amines and Carbamates; 2.1.5 Fluorination of Oxygenated Functionalities with Sulfur Tetrafluoride; 2.1.6 Fluorination of Oxygenated Functionalities with Difluoramine; 2.1.7 Introduction of Fluorine by Nitroalkane - Fluoride Reactions; 2.1.7.1 Displacement of Nitro Groups; 2.1.7.2 Displacement of Other Groups; 2.1.8 Nitrofluorination of Olefins; 2.2 Fluoronitro Alicyclics by Partial and Complete Saturation of Aromatic Structures; 2.2.1 Fluorination of Aromatics; 2.2.2 Nitrofluorination of Aromatics; 2.2.3 Nitration of Aromatics; 2.2.4 Meisenheimer Complexes; 2.2.5 Miscellaneous Reactions; 2.3 Introduction of the Nitro Group; 2.3.1 Reaction of Fluoroolefins with Dinitrogen Tetroxide; 2.3.2 Reaction of Fluoroolefins with Dinitrogen Trioxide; 2.3.3 Reaction of Fluoroolefins with Nitric Oxide; 2.3.4 Reaction of Fluoroolefins with Nitrosyl Halides; 2.3.5 Reaction of Various Fluoroalkyl Compounds with Oxides of Nitrogen; 2.3.5.1 Carboxylic Acids; 2.3.5.2 Diazirine and Diazo Compounds; 2.3.6 Nitration of Fluoroolefins; 2.3.6.1 Nitric Acid--Sulfuric Acid; 2.3.6.2 Nitric Fluorosulfonic Anhydride; 2.3.7 Nitration of Fluoroalkanes and Fluoroacids with Nitric Acid; 2.3.8 Nitration of Fluoroalkyl Amines; 2.3.9 Nitration of N--Fluoro--N--Alkyl Carbamates; 2.3.10 Oxidation of Nitrogen Functionalities in Fluorocarbons; 2.3.10.1 Oxidation of Fluoroalkyl Nitroso Compounds; 2.3.10.2 Oxidation of Amines, Oximes, and Nitriles; 2.3.11 Addition and Displacement Reactions of Nitrite Ion with Fluoroolefins and Halofluoroalkanes; 2.3.11.1 Fluoroolefins; 2.3.11.2 Fluoroalkyl Halides; 2.4 Condensation and Addition Reactions Between Nitroaliphatic Compounds and Fluorocarbon Derivatives; 2.4.1 Reaction of Fluorinated Aldehydes and Ketones with Nitroalkanes; 2.4.1.1 Dehydration of Products of the Henry Reaction to Fluoronitroolefins; 2.4.2 Fluoronitroaliphatic Compounds by Addition Reactions to Activated Olefins; 2.4.3 Reaction of Fluoroalkylamines with Nitroalcohols; 2.4.4 Miscellaneous Reactions for Coupling Nitroalkanes to Fluoroalkyl Iodides and Sulfenyl Chlorides; III. Chemical Transformations of Fluoronitro Compounds; 3.1 Reaction of Fluoronitrocarbons Involving a C - halogen or C - NO 2 Bond; 3.2 Reactions of Fluoronitrocarbons Involving a Nitro--Activated C - H Bond; 3.2.1 Acidity of Fluoronitromethanes; 3.2.2 Salts of Fluoronitromethanes; 3.2.3 Carbonyl Addition Reactions of Fluoronitromethanes; 3.2.4 Michael Addition of Fluoronitromethanes; 3.2.5 Mannich Reaction of Fluoronitromethanes; 3.2.6 Miscellaneous Reactions of Fluoronitromethanes; 3.2.7 Some Reactions of 2--Fluoro--1--nitroalkanes; 3.2.8 Some Reactions of 3--Fluoro--1--nitroalkanes; 3.3 Reactions of Fluoronitroalcohols; 3.3.1 Acylation of Fluoronitroalcohols; 3.3.2 Ethers, Acetals, and Orthoesters by Alkylation of Fluoronitroalcohols; 3.3.3 Fluoronitroalcohols in the Mannich Reaction; 3.3.4 Addition of Fluoronitroalcohols to Multiple Bonds; 3.3.5 Dehydration of Fluoronitroalcohols; 3.3.6 Oxidation of Fluoronitroalcohols; 3.3.7 Demethylolation of Fluoronitroalcohols; 3.3.8 Displacement of the Hydroxyl Group in Fluoronitroalcohols; 3.4 Reactions of Fluoronitrocarboxylic Acids and Their Derivatives; 3.4.1 Acids, Acid Chlorides, and Anhydrides; 3.4.2 Esters, Amides; 3.4.3 Nitriles, Amidines; 3.5 Reactions of Fluoronitroalkyl Amines and of Some Derivatives; 3.5.1 Acylation; 3.5.2 Mannich and Related Condensation Reactions with Fluoronitro Alkylamines; 3.5.3 Nitration and Nitrosation of Fluoronitro Alkylamines and Amides; 3.5.4 Oxidation of 2,2,2--Fluorodinitroethylamines; 3.5.5 Miscellaneous Reactions of Fluoronitro Alkylamine Derivatives; 3.5.5.1 Isocyanates and Carbamates; 3.5.5.2 Nitramines; 3.5.5.3 Dealkylation of N--Alkyl--bis(2,2,2--fluorodinitroethyl)amines; 3.6 Reactions of Fluoronitro Carbonyl Compounds; 3.6.1 Additions to the Carbonyl Group; 3.6.1.1 Cycloadditions; 3.6.1.2 Additions of X - H; 3.6.1.3 Other Addition Reactions; 3.6.2 Carbonyl Addition Reactions Resulting in Fragmentation; 3.6.3 Reduction of Fluoronitroketones; 3.6.4 Miscellaneous Reactions of Fluoronitroketones; 3.7 Reactions of Fluoronitro Nitroso Compounds; 3.7.1 Reactions of Fluoronitro Nitroso Compounds with Enes and Dienes; 3.7.2 Hydrolysis of Tetrafluoro--2--nitro--1--nitrosoethane; 3.7.3 Condensation of Fluoronitro Nitroso Compounds with Amines; 3.7.4 Miscellaneous Reactions of Fluoronitro Nitroso Compounds; 3.8 Reactions of Fluoronitroalcohol Derivatives; 3.8.1 Some Displacement Reactions of Fluoronitroalkyl Sulfonates; 3.8.2 Reactions of Chloromethyl Fluorodinitroethyl Ether; 3.8.3 Addition and Oxidation Reactions of Fluorodinitroethyl Vinyl, Allyl, and Glycidyl Ethers; 3.8.4 Unsymmetrical Orthocarbonates and Formates from Tris(fluoronitroethoxy)methyl Disulfides via Tris(fluoronitroethoxy)chloromethanes; 3.8.5 Miscellaneous Reactions; 3.9 Reactions of Nitrofluoroalkyl Nitrites; 3.10 Reactions of Fluoronitroolefins; 3.10.1 Reduction of Fluoronitroolefins; 3.10.2 Reaction with Dienes; 3.10.3 Other Addition Reactions to Fluoronitroolefins; 3.10.4 Oxidation of Fluoronitroalkenes; 3.11 Miscellaneous Reactions of Fluoronitro Compounds; IV. Molecular and Spectral Properties of Fluoronitro Compounds; 4.1 General Physical Properties; 4.2 General Chemical Properties; 4.3 X--ray Diffraction and Other Structural Data of Fluoronitro Compounds; 4.4 Nuclear Magnetic Resonance Spectral Data of Fluoronitro Compounds; 4.4.1 1 H NMR Spectra of Fluoronitroalkanes; 4.4.1.1 Fluoronitromethanes; 4.4.1.2 2--Fluoro--1--nitroalkanes; 4.4.1.3 2--H-- and 3--H--1,1--Fluoronitroalkanes; 4.4.2 19 F NMR Spectra of Fluoronitroalkanes; 4.4.2.1 Fluoronitromethanes; 4.4.2.2 Fluorodinitromethanes; 4.4.2.3 1,2--Fluoronitro Compounds; 4.4.2.4 1,3-- and Other Fluoronitro Compounds; 4.4.3 13 C and 14 N NMR Spectra of Fluoronitroalkanes; 4.5 Infrared Spectra of Fluoronitro Compounds; 4.5.1 C - F Stretching Frequencies of Fluoronitro Compounds; 4.5.1.1 Fluoronitromethanes; 4.5.1.2 Fluorodinitromethanes; 4.5.1.3 1,2--, 1,3--, and Other Fluoronitroalkanes; 4.5.2 N - O Infrared Stretching Frequencies of Fluoronitro Compounds; 4.5.2.1 Fluoronitromethanes; 4.5.2.2 Difluoronitromethanes; 4.5.2.3 Fluorodinitromethanes; 4.5.2.4 1,2--and 1,3--Fluoronitroalkanes; 4.5.2.5 Fluoroalkyl Nitramines; Acknowledgments; References; Author Index