Nitro Compounds

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