Practical catalytic nitration directly with commercial nitric acid for the preparation of aliphatic nitroesters

An, Jichao; Li, Peipei; Si, Mengyuan; Li, Wenhao; He, Pan; Bo, Yang; Yang, Ge

doi:10.1039/d0ob01519a

Cited by 6 publications

(6 citation statements)

References 22 publications

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“…This is supported by FTIR evidence for the formation of −ONO 2 groups from the reaction of NO 2 + with both 1-octanol and methyl-10-undecenonate and the absence of a strong organic nitrate signature following the reaction of methyl palmitate, which is an aliphatic methyl ester without −OH or CC functional groups. The formation of organic nitrates from the reaction of alcohols with NO 2 + sources such as nitric acid and N 2 O 5 has been reported in the literature. ,, Kames et al report producing small quantities of organic nitrates by reacting alcohols with N 2 O 5 . Another process that likely contributes to the formation of RONO 2 in NOM samples is suggested by the abundant formation of carboxylic acid products in the methyl ester model compounds studied.…”

Section: Resultsmentioning

confidence: 82%

“…This suggests that the OH group of 1-octanol is replaced by an organic nitrate, likely via the reaction of NO 2 + with the terminal OH group (Figure , R8). O -Nitration of alcohols by concentrated HNO 3 (via NO 2 + ) is a well-known approach to synthesizing organic nitrates. ,, In addition, the same procedure is often used to oxidize aliphatic alcohol groups to carboxylic acids via organic nitrate intermediates (R8), which may contribute to the appearance of −COOH groups in Figure b.…”

Section: Resultsmentioning

confidence: 99%

“…) is a well-known approach to synthesizing organic nitrates. 1,58,59 In addition, the same procedure is often used to oxidize aliphatic alcohol groups to carboxylic acids via organic nitrate intermediates (R8), 60 which may contribute to the appearance of −COOH groups in Figure 5b.…”

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confidence: 99%

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Reaction of Organic Matter with Nitronium Ion as a Source of Organic Nitrate Esters in Proxies for Organic Aerosols

Hansen,

Dalton,

Abney

et al. 2023

ACS Earth Space Chem.

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Organic nitrate ester compounds (RONO2) are an important sink for nitrogen oxides (NO x ≡ NO + NO2) that impact ozone and organic aerosol formation in the lower atmosphere. While RONO2 formation from gas phase oxidation chemistry and heterogeneous reactions involving reactive uptake of NO3 into organic aerosols is well documented, in situ bulk-aqueous-phase production of RONO2 within organic aerosols has not been explored as extensively. Here, we provide evidence that RONO2 species are produced during aqueous phase reactions of nitronium (NO2 +) with humic and fulvic acids, which are used as surrogates for aerosol organic matter. X-ray photoelectron spectroscopy (XPS) and high-resolution mass spectrometry were used to characterize nitrogen functional groups and changes in bulk chemical composition during nitration reactions. Correlations between the organic N abundance in reacted humic and fulvic acids and functional group abundance measured by solid-state 13C NMR indicate that NO2 + targets the lipid fraction of the organic matter. Fourier transform infrared spectroscopy (FTIR) analysis of model lipid compounds shows that the reaction of NO2 + with terminal alcohols (ROH) and alkenes is a source of stable RONO2 compounds. Further, the low-pH environment of most nitrate aerosols is expected to enhance the total terminal ROH pool through acid-catalyzed ester hydrolysis within the lipid-like fraction of natural organic matter. Our findings demonstrate that multiphase oxidation of organic matter by NO2 +, along with air-particle partitioning of products from gas-phase chemistry, may be an important source of particle-phase organic nitrates.

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Section: Resultsmentioning

confidence: 82%

Section: Resultsmentioning

confidence: 99%

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Reaction of Organic Matter with Nitronium Ion as a Source of Organic Nitrate Esters in Proxies for Organic Aerosols

Hansen,

Dalton,

Abney

et al. 2023

ACS Earth Space Chem.

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“…At present, there are few research reports in this area. Therefore, in this study, combined with the high-throughput synthesis platform developed by the research group, oxidation reactions [11][12][13][14][15] , nitration reactions [16][17][18][19] , as well as ion exchange reactions [20][21][22][23][24][25] were studied. Although there is no technical difficulty in handling the synthesized energetic salts described in this paper, they should be handled with extreme care using the best safety practices (face shield, gloves, 2.1.…”

Section: Introductionmentioning

confidence: 99%

Research on Integrated Parallel Reactions for the High Throughput Preparation Energetic Materials

Wang

Zhou

et al. 2023

J. Phys.: Conf. Ser.

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The high-throughput automatic sample addition platform technology was applied to the large-scale sample addition, pretreatment, and high-throughput synthesis of simple compounds in many fields. With the introduction of material genome technology into the field of high energy energetic materials (HEDMs), the energetic materials genome (EMG) project is implemented. Completing different reaction types at the same time has become key to high-throughput synthesis of energetic materials. In this study, three common synthetic methods (nitration, oxidation and ion exchange reactions) were selected and successfully integrated on the high-throughput automatic sample addition platform. The parallel reactions could be used for preparing energetic materials. The method is viable for high-throughput synthesis of HEDMs. The method improves the efficiency, safety, labor costs compared to conventional methods, which is of great significance for accelerating the synthesis of HEDMs.

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“…2-Ethylhexyl nitrate is used primarily as a diesel additive to increase the diesel cetane number, improve combustion performance, reduce ignition delay time, and improve engine power performance. − Yet to date, the industrial production of 2-ethylhexyl nitrate is usually based on the nitration of 2-ethyl-1-hexanol with mixed acid in batch reactors, which is highly exothermic. Generally speaking, 2-ethylhexyl nitrate is a heat-sensitive and high-energy substance, and temperature control during the reaction is essential.…”

Section: Introductionmentioning

confidence: 99%

Scale-Up and Development of Synthesis 2-Ethylhexyl Nitrate in Microreactor Using the Box–Behnken Design

Guo

Zhan

Zhu

et al. 2021

Org. Process Res. Dev.

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In this study, kilogram-scale synthesis of 2-ethylhexyl nitrate in a microreactor was reported. Using Box–Behnken experimental design, the effects of process parameters such as temperature, molar ratio, total flow rate, and mass fraction of sulfuric acid on the yield of the target product were systematically investigated. The experimental design was studied at four factors and three levels. The results revealed that the sulfuric acid mass fraction and temperature significantly affected the yield of the product. There was a good agreement between the experimental results and predicted results by the proposed regression model. Subsequently, the mixing effect of the liquid–liquid heterogeneous system in microreactor was simulated by using computational fluid dynamics. The results provide solid evidence that the microreactor has excellent mixing efficiency in mass and heat transfer compared with the conventional reactor. Consequently, based on the results of process parameter optimization, an enlarged microreactor was designed to intensify the preparation of 2-ethylhexyl nitrate by a throughput of 16 kg/h.

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Practical catalytic nitration directly with commercial nitric acid for the preparation of aliphatic nitroesters

Abstract: To pursue a sustainable and efficient approach for aliphatic nitroester preparation from alcohol, Europium triflate-catalyzed nitration, that directly used commercial nitric acid, has been successfully developed. Gram scalability with operational...

Cited by 6 publications

References 22 publications

Reaction of Organic Matter with Nitronium Ion as a Source of Organic Nitrate Esters in Proxies for Organic Aerosols

Reaction of Organic Matter with Nitronium Ion as a Source of Organic Nitrate Esters in Proxies for Organic Aerosols

Research on Integrated Parallel Reactions for the High Throughput Preparation Energetic Materials

Scale-Up and Development of Synthesis 2-Ethylhexyl Nitrate in Microreactor Using the Box–Behnken Design

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