Generation of methylene by the liquid phase oxidation of isobutene with nitrous oxide

Семиколенов, С. В.; Иванов, Д. П.; Babushkin, Dmitrii E.; Malykhin, S. E.; Харитонов, А. С.; Дубков, К. А.

doi:10.1016/j.tet.2018.05.022

Cited by 9 publications

(35 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The composition of reaction products is consistent with the mechanism of 1,3-dipolar cycloaddition of N 2 O to the CC double bond of olefins. ,,,− According to this nonradical mechanism, N 2 O reacts with olefins via an unstable 4,5-dihydro[1,2,3]oxadiazole intermediate. Its subsequent decomposition with the release of N 2 yields a carbonyl product.…”

Section: Resultssupporting

confidence: 72%

“…In particular, the liquid-phase oxidation of propylene with nitrous oxide at 493 K leads to similar carbonyl products (acetone, propanal, and acetaldehyde), methylcyclopropane, and also cycloheptatriene formed by the addition of methylene to the aromatic ring of benzene . As we have shown earlier, an especially high yield of methylene is achieved in the liquid-phase oxidation of isobutene with nitrous oxide . The quantum-chemical simulation shows that the oxidation of olefins with nitrous oxide leads to the formation of singlet methylene because the ground state of the reactants is also singlet …”

Section: Resultsmentioning

confidence: 55%

See 1 more Smart Citation

Gas-Phase Oxidation of a Propane–Propylene Mixture by Nitrous Oxide

Дубков

Parfenov

Харитонов

2020

Ind. Eng. Chem. Res.

View full text Add to dashboard Cite

The present study focuses on a new method for obtaining C2−C3 carbonyl compounds (ketones and aldehydes) by the gas-phase selective oxidation of a propane−propylene mixture using nitrous oxide (N 2 O). The oxidation is carried out without catalyst in the temperature range of 623−773 K at elevated pressure. The obtained results reveal that only propylene in the propane− propylene mixture reacts with nitrous oxide. The reaction proceeds by the nonradical mechanism involving the 1,3-dipolar cycloaddition of N 2 O to the CC double bond of olefin. The main reaction products are acetone, propanal, and acetaldehyde. At 723 K and a pressure of 0.7 MPa, the total selectivity to these products amounts to 74.6%, the N 2 O conversion attains 74.5%, and the propylene conversion is 12.5%. An important feature of the reaction is the additional formation of methylcyclopropane with a selectivity of ca. 6%.

show abstract

Section: Resultssupporting

confidence: 72%

Section: Resultsmentioning

confidence: 55%

Gas-Phase Oxidation of a Propane–Propylene Mixture by Nitrous Oxide

Дубков

Parfenov

Харитонов

2020

Ind. Eng. Chem. Res.

View full text Add to dashboard Cite

show abstract

“…Note that the reaction of individual olefins with N 2 O can also proceed via the cleavage of C–C bonds in the 4,5-dihydro-[1,2,3]-oxadiazole intermediate (Scheme ) with the formation of small amounts of methylene/CH 2 (in the case of terminal olefins) or alkyl carbenes/CHR. ,,,, The carbenes can readily react with parent olefins, yielding cyclopropane derivatives, which are the typical minor products of the reaction. ,− ,,, In addition, carbenes can insert into C–H bonds and aromatic rings of hydrocarbons, which can also lead to the formation of additional products upon oxygenation of LCCG.…”

Section: Resultsmentioning

confidence: 99%

“…33,35,37,39,43 The carbenes can readily react with parent olefins, yielding cyclopropane derivatives, which are the typical minor products of the reaction. 31,[33][34][35]37,39,43 In addition, carbenes can insert into C−H bonds and aromatic rings of hydrocarbons, 54 which can also lead to the formation of additional products upon oxygenation of LCCG. 3.2.…”

Section: Resultsmentioning

confidence: 99%

“…The oxidation of olefins with N 2 O proceeds thermally (without a catalyst) at a temperature above 453–473 K with selectivity often exceeding 90%. − In contrast to molecular oxygen, nitrous oxide reacts solely with the double bonds of olefins via a nonradical mechanism involving the 1,3-dipolar cycloaddition of N 2 O molecules to the CC bond (Scheme ). ,,,− Subsequent decomposition of the unstable 4,5-dihydro-[1,2,3]-oxadiazole intermediate leads to ketone or aldehyde. This prevents further oxidation of the reaction products and allows selective oxidation of olefins in the mixture with paraffins, naphthenes, and aromatic hydrocarbons.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Reducing the Olefin Content in Light Fluid Catalytic Cracking Gasoline by Treatment with Nitrous Oxide

Дубков

Семиколенов

Иванов

et al. 2021

Ind. Eng. Chem. Res.

View full text Add to dashboard Cite

Nitrous oxide (N 2 O) is a greenhouse gas with high global warming potential. Currently, only a small part of concentrated industrial N 2 O emissions is used to obtain valuable chemical products. Most of these emissions are neutralized by thermal or catalytic decomposition, which is associated with additional costs and, in the case of a thermal process, is accompanied by the formation of significant amounts of carbon dioxide. In the present work, nitrous oxide was used for the first time for the oxidative treatment of light catalytic cracked gasoline (LCCG). LCCG is one of the blending components of motor gasoline. However, it contains a significant amount of olefins, which negatively affects the storage stability of fuel. The conversion of olefins into oxygenates is one of the promising approaches to improving the performance of gasoline fuels. The treatment of LCCG with N 2 O was performed noncatalytically in the liquid phase at 473−523 K and elevated pressure. Under these conditions, N 2 O selectively oxidizes only olefinic compounds in LCCG to form carbonyl products (mainly ketones) and molecular nitrogen without affecting other components of LCCG. An increase in the content of oxygen, which was introduced into gasoline from N 2 O as the carbonyl product, to 2.3 wt % is accompanied by a nearly proportional growth of antiknock indexes from 88.2 for the parent LCCG to 89.5 for the most oxygenated LCCG.

show abstract

Theoretical Study on the Gas‐Phase Oxidation Mechanism of Ethylene by Nitrous Oxide

Jiang²,

et al. 2022

Propellants Explo Pyrotec

View full text Add to dashboard Cite

The application of nitrous oxide (N 2 O) as a candidate oxidant provides a new opportunity for green propellants and propulsion systems. In this study, reaction paths are calculated by the DFT method in the B3LYP/6-31 + + G** approximation for direct oxidation of ethylene with nitrous oxide. The results indicate that the reaction between N 2 O and C 2 H 4 proceeds by a chain reaction mechanism. The reaction prefers the mechanism including 1,3-dipolar cyclo-addition of N 2 O to the double bond with the formation of unstable 4,5-dihydro-[1,2,3] oxadiazole intermediate via a transition state with an activation energy barrier of 102.54 kJ/mol, which is far below than that of N 2 O or C 2 H 4 decomposition. Subsequently, the next step is the decomposition of these intermediates through hydrogen transfer within the hydrocarbon backbone and the formation of the final products.

show abstract

Generation of methylene by the liquid phase oxidation of isobutene with nitrous oxide

Cited by 9 publications

References 49 publications

Gas-Phase Oxidation of a Propane–Propylene Mixture by Nitrous Oxide

Gas-Phase Oxidation of a Propane–Propylene Mixture by Nitrous Oxide

Reducing the Olefin Content in Light Fluid Catalytic Cracking Gasoline by Treatment with Nitrous Oxide

Theoretical Study on the Gas‐Phase Oxidation Mechanism of Ethylene by Nitrous Oxide

Contact Info

Product

Resources

About