Electrochemical Nitration with Nitrite

Blum, Stephan P.; Nickel, Christean; Schäffer, Lukas; Karakaya, Tarik; Waldvogel, Siegfried R.

doi:10.1002/cssc.202102053

Cited by 22 publications

(18 citation statements)

References 96 publications

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“…222 In 2021, the Waldvogel group showed that tetrabutylammonium nitrite is also a safe NO 2 source in the electrochemical nitration of aromatic compounds 388 (Scheme 107). 223 The reaction proceeded mainly with electron-rich arenes; the yields were significantly dependent on the na-ture of the substrate. According to the postulated mechanism, initial anodic oxidation of nitrite to NO 2 , which is in equilibrium with N 2 O 4 , takes place.…”

Section: Organic Nitritesmentioning

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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Section: Organic Nitritesmentioning

confidence: 99%

Organic Nitrating Reagents

Patra¹,

Mosiagin²,

Katayev³

et al. 2022

Synthesis

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“…Therefore, we are quite interested in the possibility of developing a new nitration reagent based on this hoststructure. The preparation of dinitro-5,5-dimethylhydantoin (DNDMH, 11) was readily achieved by the treatment of 5,5dimethylhydantoin (12) with ammonium nitrate and trifluoroacetic anhydride (Scheme 1). And the structure of 11 was unambiguously determined through X-ray crystallography (CCDC 2252101).…”

mentioning

confidence: 99%

“…Using the traditional conditions, the mixed nitric–sulfuric acid presents distinct disadvantages of inferior functional group tolerance, poor position selectivity, and formation of byproducts from oxidation or hydrolysis . In recent decades, divergent strategies for nitration of arenes have been developed, which include oxidation of aryl azides or anilines, ipso -nitration of prefunctionalized arenes, transition metal catalyzed cross-coupling, directed C–H activation, electrochemical, photochemical, and enzymatic nitrations …”

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confidence: 99%

Dinitro-5,5-Dimethylhydantoin: An Arene Nitration Reagent

Jia

2023

Org. Lett.

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The development of a new N-nitro type compound, dinitro-5,5-dimethylhydantoin (DNDMH), has been reported as an arene nitration reagent. The exploration demonstrated that arene nitration with DNDMH exhibited good tolerance with diverse functional groups. It is notable that, among the two N-nitro units of DNDMH, only the N-nitro unit on N1 was delivered to the nitroarene products. The N-nitro type compound with a single N-nitro unit on N2 cannot promote the arene nitration.

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“…15 Hexafluoroisopropanol (HFIP) also shows excellent performance in electrophilic nitration reactions. 16 For example, Hua and co-workers developed a simple nitrating system for the nitration of arenes at room temperature by using 1 equiv of nitric acid in HFIP (Scheme 1d). 17 The solvent HFIP can be easily recycled, and the only byproduct is water.…”

mentioning

confidence: 99%

Trifluoromethanesulfonic Acid Promoted Controllable Electrophilic Aromatic Nitration

et al. 2023

J. Org. Chem.

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In this work, we developed a facile and controllable electrophilic aromatic nitration method with commercially available 68% HNO 3 as the nitrating reagent and trifluoromethanesulfonic acid (HOTf) as the catalyst in hexafluoroisopropanol or under solvent-free conditions. The electrophilic nitration products of different arenes can be obtained in almost quantitative yields by tuning the loading of HOTf. The strong acidity and water absorbing property of HOTf allowed this transformation to reach completion in a short time at room temperature.

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Electrochemical Nitration with Nitrite

Abstract: Scheme 1. Selected approved drugs containing nitro functionalities.Scheme 2. Traditional approach (electrophilic aromatic substitution) in comparison to the electrochemical nitration with nitrite (this work); C gr = graphite.

Cited by 22 publications

References 96 publications

Organic Nitrating Reagents

Organic Nitrating Reagents

Dinitro-5,5-Dimethylhydantoin: An Arene Nitration Reagent

Trifluoromethanesulfonic Acid Promoted Controllable Electrophilic Aromatic Nitration

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