Green Chlorobenzene nitration by ultrasonic-assisted synthesized sulfated ZrO2 catalyst with NO2 DOI Creative Commons

Renjie Deng,

Haishuai Cui,

Meilin Liu

et al.

Research Square (Research Square), Journal Year: 2023, Volume and Issue: unknown

Published: Jan. 31, 2023

Abstract Different solid superacid sulfated ZrO 2 (SO 4 2- /ZrO ) samples were successfully prepared by conventional and ultrasonic assisted chemical precipitation process, then they characterized XRD, FT-IR, TGA, BET, NH 3 -TPD Py-FT-IR. The results indicate that the acidity surface area of sample can be increased using ultrasonic. Furthermore, this ultrasonic-assisted catalyst was used for chlorobenzene nitration NO as nitrating agent. shows excellent catalytic activity reusability giving high para selectivity. reaction mechanism proposed combination experimental theoretical calculations. present work provides an easy-to-implement, mild environmentally friendly approach efficient preparation valuable -nitrochlorobenzene, which has extensive industrial application prospects.

Language: Английский

Organic Nitrating Reagents DOI
Subrata Patra, Ivan Mosiagin, Dmitry Katayev

et al.

Synthesis, Journal Year: 2022, Volume and Issue: 54(15), P. 3432 - 3472

Published: April 13, 2022

Abstract Nitro compounds are vital raw chemicals that widely used in academic laboratories and industries for the preparation of various drugs, agrochemicals, materials. Thus, nitrating reactions great importance chemists even taught schools as one fundamental transformations organic synthesis. Since discovery first 19th century, progress this field has been constant. Yet, many years classical electrophilic nitration approach using a mixture strong mineral acids dominated field. However, recent decades, attention researchers focused on new reactivity reagents can provide access to nitro practical straightforward way under mild reaction conditions. Organic have played special role since they enhanced reactivity. They also allow be carried out an ecofriendly sustainable manner. This review examines development application reagents. 1 Introduction 2 Nitrating Reagents 2.1 Alkyl Nitrites 2.2 Nitroalkanes 2.3 Nitrates 2.4 N-Nitroamides 2.5 N-Nitropyrazole 2.6 N-Nitropyridinium Salts 3 Generated In Situ 3.1 Acyl 3.2 Trimethylsilyl Nitrate 3.3 Onium 4 Nitronium 5 5.1 Ammonium 5.2 Heteroarylium 5.3 Other 5.4 6 Conclusion Outlook

Language: Английский

Citations

42
The green chemistry paradigm in modern organic synthesis DOI
Sergei G. Zlotin, Ksenia S. Egorova, Valentine P. Ananikov

et al.

Russian Chemical Reviews, Journal Year: 2023, Volume and Issue: 92(12), P. RCR5104 - RCR5104

Published: Dec. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Language: Английский

Citations

40
Dual Roles of Supporting Electrolytes in Organic Electrosynthesis DOI Creative Commons

Lilla G. Gombos,

Joachim Nikl,

Siegfried R. Waldvogel

et al.

ChemElectroChem, Journal Year: 2024, Volume and Issue: 11(8)

Published: Jan. 18, 2024

Abstract Synthetic electro‐organic chemistry is advancing to a well‐established methodology in academic research and industry. The simple process control minimizes reagent waste avoids using toxic environmentally unfriendly redox agents, providing feasible sustainable alternative conventional techniques. However, fundamental disadvantage, the necessity of ion‐conductive components within electrolyte. recovery these supporting electrolytes, as well product isolation, pose challenges for work‐up strategies. This review presents following electrochemical protocols featuring material‐ resource‐saving strategy: dual role electrolytes conductivity enabling reagents or meditators. first conclude categorize strategies electrolytes. It may inspire electrochemists advance development optimization synthesis towards more resource‐efficient reaction control.

Language: Английский

Citations

16
Electron‐Driven Nitration of Unsaturated Hydrocarbons DOI Creative Commons
Subrata Patra, Ivan Mosiagin, Rahul Giri

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(28)

Published: April 25, 2023

Herein, we introduce an electrochemically assisted generation of nitryl radicals from ferric nitrate under mild reaction conditions using a simple setup with inexpensive graphite and stainless-steel electrodes. The mechanism the is supported by detailed spectroscopic experimental studies. Powered electricity driven electrons, synthetic diversity this has been demonstrated through development highly efficient nitration protocols various unsaturated hydrocarbons. In addition to broad application area, these are easy scale for decagram quantities, exhibit exceptional substrate generality functional-group compatibility.

Language: Английский

Citations

19
From N–H Nitration to Controllable Aromatic Mononitration and Dinitration─The Discovery of a Versatile and Powerful N-Nitropyrazole Nitrating Reagent DOI Creative Commons
Tao Yang, Xiaoqian Li, Shuang Deng

et al.

JACS Au, Journal Year: 2022, Volume and Issue: 2(9), P. 2152 - 2161

Published: Aug. 31, 2022

Nitroaromatics are tremendously valuable organic compounds with a long history of being used as pharmaceuticals, agrochemicals, and explosives well vital intermediates to wide variety chemicals. Consequently, the exploration aromatic nitration has become an important endeavor in both academia industry. Herein, we report identification powerful nitrating reagent, 5-methyl-1,3-dinitro-1H-pyrazole, from N-nitro-type reagent library constructed using practical N-H method. This behaves controllable source nitronium ion, enabling mild scalable broad range (hetero)arenes good functional group tolerance. Of note, our method could be controlled by manipulating reaction conditions furnish mononitrated or dinitrated product selectively. The value this medicinal chemistry been established its efficient late-stage C-H complex biorelevant molecules. Density theory (DFT) calculations preliminary mechanistic studies reveal that powerfulness versatility due synergistic "nitro effect" "methyl effect".

Language: Английский

Citations

26
Catalytic ipso‐Nitration of Organosilanes Enabled by Electrophilic N‐Nitrosaccharin Reagent DOI Creative Commons
Ivan Mosiagin, Anthony J. Fernandes, Alena Budinská

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)

Published: Aug. 26, 2023

Nitroaromatic compounds represent one of the essential classes molecules that are widely used as feedstock for synthesis intermediates, preparation nitro-derived pharmaceuticals, agrochemicals, and materials on both laboratory industrial scales. We herein disclose efficient, mild, catalytic ipso-nitration organotrimethylsilanes, enabled by an electrophilic N-nitrosaccharin reagent allows chemoselective nitration under mild reaction conditions, while exhibiting remarkable substrate generality functional group compatibility. Additionally, conditions proved to be orthogonal other common functionalities, allowing programming molecular complexity via successive transformations or late-stage nitration. Detailed mechanistic investigation experimental computational approaches strongly supported a classical aromatic substitution (SE Ar) mechanism, which was found proceed through highly ordered transition state.

Language: Английский

Citations

14
Selective Arene Photonitration via Iron-Complex β-Homolysis DOI Creative Commons

Shuyang Liu,

Ziyu Gan, Min Jiang

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(12), P. 4899 - 4909

Published: Nov. 21, 2024

Nitroaromatics, as an important member and source of nitrogen-containing aromatics, is bringing enormous economic benefits in fields pharmaceuticals, dyes, pesticides, functional materials, fertilizers, explosives. Nonetheless, the notoriously polluting nitration industry, which suffers from excessive discharge fumes waste acids, poor group tolerance, tremendous purification difficulty, renders mild, efficient, environmentally friendly a formidable challenge. Herein, we develop visible-light-driven biocompatible arene C–H strategy with good efficiency regioselectivity, marvelous substrate applicability wide application scale-up synthesis, total late-stage functionalization. A nitryl radical delivered through unusual β-homolysis photoexcited ferric-nitrate complex proposed to be key nitrification reagent this system.

Language: Английский

Citations

6
Electrochemical Oxidative Cleavage of Alkynes to Carboxylic Acids DOI Open Access
Qingyuan Feng, Yamin Wang,

Binnan Zheng

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(1), P. 293 - 297

Published: Jan. 1, 2023

A sustainable method for converting terminal alkynes into their corresponding carboxylic acids is reported using synthetic electrolysis in an undivided cell at room temperature. This protocol, avoiding transition metal catalysis and stoichiometric chemical oxidants, tolerates a variety of aryl, heteroaryl, alkyl akynes. Preliminary mechanistic studies demonstrate that sodium nitrite serves triple role as the electrolyte, nitryl radical precursor, nitrosating reagent.

Language: Английский

Citations

12
Dinitro-5,5-Dimethylhydantoin: An Arene Nitration Reagent DOI

F. Y. Jia,

Ao Li, Xiangdong Hu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(25), P. 4605 - 4609

Published: June 15, 2023

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

Language: Английский

Citations

12
Electrochemical Nitration with Nitrite DOI Creative Commons

Stephan P. Blum,

Christean Nickel,

Lukas Schäffer

et al.

ChemSusChem, Journal Year: 2021, Volume and Issue: 14(22), P. 4936 - 4940

Published: Sept. 28, 2021

Aromatic nitration has tremendous importance in organic chemistry as nitroaromatic compounds serve versatile building blocks. This study represents the electrochemical aromatic with NBu

Language: Английский

Citations

24