Synthesis and Performance of Cyclopentadiene-Based Spirocyclopropane High-Energy-Density Fuels

Wang, Wei; Shen, Zhensheng; Zhang, Jiaxiang; Pan, Lun; Shi, Chengxiang; Zhang, Xiangwen; Zou, Ji‐Jun

doi:10.1016/j.fuel.2023.129380

Cited by 6 publications

(2 citation statements)

References 28 publications

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“…Acid is expected to improve the electrophilicity of zinc carbenoid by reducing electron density of the −CH 2 − group. As shown in Scheme 1, the cyclopropanated products of DCPD are the bicyclic product as the ultimate product and the monocyclic products as intermediates, 18 without any other byproducts (see Figure S1). Here, we assess the reaction efficiency by the conversion of DCPD and the yield of the bicyclic product.…”

Section: Dft Calculationsmentioning

confidence: 99%

“…The cyclopropanation of one CC bond can increase the density by ca. 0.02–0.07 g/cm 3 compared to the hydrogenation of CC bond. , Indeed, several fuels with higher density, calorific value, and specific impulse than currently used missile fuel like JP-10 and rocket fuel like RP-1 have been synthesized using the cyclopropanation reaction of cyclic alkenes such as cyclopentene, norbornene, and pinene. ,− …”

Section: Introductionmentioning

confidence: 99%

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Zeolite Catalytic Simmons–Smith Cyclopropanation of Alkenes for the Synthesis of High-Energy-Density Fuels

Liu,

Yang,

Wang

et al. 2024

Ind. Eng. Chem. Res.

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Simmons−Smith cyclopropanation of alkenes is a universal reaction used to construct cyclopropyl groups in the synthesis of fine chemicals, medicines, and high-energy-density aerospace fuels. Organic acids such as trifluoroacetic acid (CF 3 COOH) are widely used to improve the reaction, but they have the disadvantages of being difficult to recycle and harmful to health and the environment. In this work, we reported that heterogeneous acidic zeolite can replace organic acids to catalyze the Simmons−Smith cyclopropanation with better activity. HZSM-5 shows higher conversion and yield than CF 3 COOH in the cyclopropanation of dicyclopentadiene and can be reused for recycled reaction. A catalytic mechanism involving Bro̷ nsted acid sites [Si(OH)Al] as the catalytic sites is proposed, which is verified by characterizations of a complex of zeolite with reactant in each step. Density functional theory (DFT) calculations show that HZSM-5 can reduce the energy barrier compared to CF 3 COOH, which explains why zeolite is more active. Activity assessment of different types of zeolites indicates that the amount of Bro̷ nsted acid sites is the key factor for cyclopropanation, and simple ball-milled HZSM-5 can further improve the activity because more acid sites are accessible for the reaction. Moreover, the zeolite performs well in the cyclopropanation of several cyclic and linear alkenes, especially for the synthesis of high-energy-density fuels, demonstrating that zeolite catalysis is a universal method to improve cyclopropanation. This work provides an efficient and environmentally friendly method for cyclopropanation.

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Section: Dft Calculationsmentioning

confidence: 99%