Nitroalkynes: A Unique Class of Energetic Materials

Windler, G. Kenneth; Pagoria, Philip F.; Vollhardt, K. Peter C.

doi:10.1055/s-0034-1378662

Cited by 11 publications

(5 citation statements)

References 88 publications

(225 reference statements)

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“…The first synthesis of nitroalkyne was achieved in 1969 by Viehe [ 25 ]. During the subsequent half century, development of the synthetic methods and studies on reactivity, as well as physical/chemical properties, has progressed [ 26 ].…”

Section: Reactivity and Applicationmentioning

confidence: 99%

A Walk through Recent Nitro Chemistry Advances

Nishiwaki

2020

Molecules

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Chemistry of nitro groups and nitro compounds has long been intensively studied. Despite their long history, new reactions and methodologies are still being found today. This is due to the diverse reactivity of the nitro group. The importance of nitro chemistry will continue to increase in the future in terms of elaborate synthesis. In this article, we will take a walk through the recent advances in nitro chemistry that have been made in past decades.

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Section: Reactivity and Applicationmentioning

confidence: 99%

A Walk through Recent Nitro Chemistry Advances

Nishiwaki

2020

Molecules

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“…1‐Nitroalkynes (nitroalkynes) are a family of molecules whose structure and high reactivity give them the potential to serve as versatile synthetic intermediates, especially for the rapid construction of nitrated heterocycles which are prevalent in anti‐microbial agents and next‐generation antibiotics . Reports on the preparation of nitroalkynes are sparse, with the first successful synthesis being achieved in 1969 by Viehe and co‐workers, when 1 was prepared by an addition‐elimination sequence (Figure ) . The nitration of alkynyl stannanes with nitronium tetrafluoroborate (NO 2 BF 4 ) and hexafluorophosphate (NO 2 PF 6 ) can be used to access alkyl‐substituted nitroalkynes 2 – 4 in moderate yields, though they are noted to rapidly decompose .…”

Section: Figurementioning

confidence: 99%

“…Reports on the preparation of nitroalkynes are sparse, with the first successful synthesis being achieved in 1969 by Viehe and co‐workers, when 1 was prepared by an addition‐elimination sequence (Figure ) . The nitration of alkynyl stannanes with nitronium tetrafluoroborate (NO 2 BF 4 ) and hexafluorophosphate (NO 2 PF 6 ) can be used to access alkyl‐substituted nitroalkynes 2 – 4 in moderate yields, though they are noted to rapidly decompose . Physical data has been recorded for 1‐nitro‐2‐phenylacetylene 5 , but a yield for its preparation (4.5 %) has only been recorded once by Kashin et al .…”

Section: Figurementioning

confidence: 99%

“…Because of our interest in nitroalkynes as building blocks for constructing biologically active heterocycles, we have set out to develop an improved, high yielding, strategy for accessing members of this class bearing a variety of substituents, both alkyl and aryl, which overcomes previous limitations caused by their instability. Low molecular weight nitroalkynes are presumed to be explosive, organo‐tin reagents are known to be toxic, and NO 2 BF 4 is considered hazardous due to its propensity to release hydrofluoric acid upon contact with water . These are issues we have also sought to address in this research.…”

Section: Figurementioning

confidence: 99%

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Synthesis and Utilization of Nitroalkyne Equivalents in Batch and Continuous Flow

Morse

Jamison

2017

Angew Chem Int Ed

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We report a method for overcoming the low stability of nitroalkynes through the development of nitrated vinyl silyltriflate equivalents. Because of their instability, nitroalkynes have only rarely been utilized in synthesis. The reactivity of these silyltriflates, which are prepared in situ, is exemplified by dipolar cycloaddition reactions with nitrones to give highly substituted 4‐nitro‐4‐isoxazolines in high yields. This approach has proven general for several different alkyl and aryl substituted alkynes. In order to minimize the accumulation of potentially hazardous reaction intermediates, we have also developed a continuous flow variant of this method that is capable of carrying out the entire reaction sequence in a good yield and a short residence time.

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“…Recent advances in the field have been documented, 11 including the progress on continuous flow nitration, 12 decarboxylative nitration, 13 safe and sustainable nitration, 11c transition-metal-catalyzed C(sp 2 )–H nitration, 14 ipso -nitration reactions, 15 and nitrative difunctionalizations. 16 In addition, several reviews cover the synthesis of nitro compounds of distinct structures, such as aliphatic 17 and aromatic 18 19 compounds, alkenes, 20 alkynes, 21 and porphyrins. 22 These reports provide a comprehensive understanding of synthetic tools currently available in the field.…”

Section: Introductionmentioning

confidence: 99%

Organic Nitrating Reagents

Patra¹,

Mosiagin²,

Katayev³

et al. 2022

Synthesis

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Nitro compounds are vital raw chemicals that are widely used in academic laboratories and industries for the preparation of various drugs, agrochemicals, and materials. Thus, nitrating reactions are of great importance for chemists and are even taught in schools as one of the fundamental transformations in organic synthesis. Since the discovery of the first nitrating reactions in the 19th century, progress in this field has been constant. Yet, for many years the classical electrophilic nitration approach using a mixture of strong mineral acids dominated the field. However, in recent decades, the attention of researchers has focused on new reactivity and new reagents that can provide access to nitro compounds in a practical and straightforward way under mild reaction conditions. Organic nitrating reagents have played a special role in this field since they have enhanced reactivity. They also allow nitration to be carried out in an ecofriendly and sustainable manner. This review examines the development and application of organic nitrating reagents.1 Introduction2 Organic Nitrating Reagents2.1 Alkyl Nitrites2.2 Nitroalkanes2.3 Alkyl Nitrates2.4 N-Nitroamides2.5 N-Nitropyrazole2.6 N-Nitropyridinium Salts3 Organic Nitrating Reagents Generated In Situ3.1 Acyl Nitrates3.2 Trimethylsilyl Nitrate3.3 Nitro Onium Salts4 Organic Nitronium Salts5 Organic Nitrates and Nitrites5.1 Ammonium Nitrates5.2 Heteroarylium Nitrates5.3 Other Organic Nitrates5.4 Organic Nitrites6 Conclusion and Outlook

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Nitroalkynes: A Unique Class of Energetic Materials

Abstract: We dedicate this paper to the memory of Professor H. G. Viehe, whose work on hetero-substituted and electron-poor alkynes was the inspiration for this review and our own investigations in the area.

Cited by 11 publications

References 88 publications

A Walk through Recent Nitro Chemistry Advances

A Walk through Recent Nitro Chemistry Advances

Synthesis and Utilization of Nitroalkyne Equivalents in Batch and Continuous Flow

Organic Nitrating Reagents

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