Nitroalkanes

Synthesis, Reactivity, and Applications

Roberto Ballini, Alessandro Palmieri

• Publisher: Wiley-VCH
• Year: 2021
• Print ISBN:
  9783527347452
• eBook ISBN:
  9783527826773
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Organic Chemistry

Discover a comprehensive exploration of recent progress in the preparation of nitroalkanes from two leading voices in the field

Nitroalkanes: Synthesis, Reactivity, and Applications delivers a thorough summary of the importance of nitroalkanes in organic synthesis. The book covers their preparation, transformation into other functional groups, like carbonyls and amines, and their use in the formation of single carbon-carbon or double carbon-carbon bonds. The distinguished authors have included chapters on acyclic and cyclic alpha-nitro ketones as well as the synthesis of cyclopropanes and spiro ketals.

The book provides treatments of the application of nitroalkanes for the synthesis of important heterocycles, poly-functionalized structures, natural products, and compounds of biological and pharmaceutical interest. A one-stop resource in a topic that hasn???t been fully addressed by any other book in decades, this book covers the most important synthetic routes toward nitroalkanes.

Readers will also benefit from the inclusion of:

• A thorough introduction to the synthesis of nitroalkanes, as well as the transformation of the nitro group into other functionalities
• An exploration of the formation of C-C single bonds, C=C double bonds, and the breaking of C3C bonds from cyclic alpha-nitro ketones
• Discussions of acyclic alpha-nitro ketones, nitroalkanes as precursors of cyclopropanes, and the synthesis of spiro ketals
• An examination of the preparation and synthetic applications of 1,3-Dinitroalkanes

Perfect for organic chemists, natural products chemists, and catalytic chemists, Nitroalkanes: Synthesis, Reactivity, and Applications will also earn a place in the libraries of medicinal chemists seeking a one-stop resource for the most recent developments in the preparation of nitroalkanes, their functionalization, and their applications.

1
Synthesis of Nitroalkanes

1.1 Synthesis of Nitroalkanes

Simple nitroalkanes (CH₃(CH₂)_0–5NO_2, c-C_5,6H_9–11NO₂, i-PrNO₂, etc.) are commercially available, while the more complex ones need to be prepared following a variety of synthetic procedure and, in this sense, there are a variety of methods to obtain a large collection of nitroalkanes.

1.1.1 Displacement of Alkyl Halides

Treatment of alkyl halides with metal nitrite is certainly the best known and the most used method for the preparation of nitroalkanes, mainly the primary ones (R¹ = H, Scheme 1.1) [1].

Scheme 1.1 Displacement (nitration) of alkyl halides.

In literature a variety of efficient procedures have been reported using sodium or silver nitrite (M = Ag, Victor-Meyer reaction [2]; M = K or Na Kornblum reaction [3]), anyway the formation of nitroalkanes is accomplished by the formation of alkyl nitrite as by-product, removed via distillation or chromatography. The nitrite is formed because of the ambident nature of the nitrite anion, which bears two different nucleophilic centers. The reaction is typically performed at room temperature adding the halide to a stirred mixture of dimethyl formamide (DMF) and metal nitrite. The use of DMF is due to the ability of this solvent to dissolve the nitrite and to accelerate the reaction of the alkali nitrite with the halide, while minimizing any side reaction such as those reported in Scheme 1.1.

An interesting application of the nitration of alkyl halides has been reported [4] for the preparation of fatty nitroalkanes, mainly the polyunsaturated ones, from naturally alcohols (Scheme 1.2) through their successive conversion into (i) bromo alkanes, (ii) iodo alkanes (more reactive vs bromo derivatives), and (iii) nitr...

Table of contents

• Cover
• Table of Contents
• Title Page
• Copyright
• Dedication
• About the Authors
• Acknowledgments
• Introduction
• List of Abbreviations
• 1 Synthesis of Nitroalkanes
• 2 Reduction of the Nitro Group into Amines
• 3 Nitro Group to Carbonyl (Nef Reaction)
• 4 Nitroaldol (Henry) Reaction
• 5 Conjugate Addition of Nitroalkanes to Electron-Poor Alkenes (Michael Reaction)
• 6 Formation of C—C Bond by Coupling Nitroalkanes with Aryl Halides
• 7 Synthesis and Reactivity of 1,3-Dinitroalkanes
• 8 Formation of Carbon=Carbon Double Bonds via Nitrous Acid Elimination (NAE)
• 9 α-Nitrocycloalkanones, Synthesis, and Reactivity
• 10 Acyclic α-Nitro Ketones: Synthesis and Reactivity
• 11 Nitro Cyclopropanes: Synthesis and Applications
• 12 Nitroalkanes as Source of Dicarbonyls
• 13 Nitroalkanes as Source of Spiroketals
• Index
• End User License Agreement