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RENEWABLE ENERGY · 2024 · IF 9

A high-performance liquid biofuel produced from biomass-derived 2-cyclopentenone as an intermediate

Cuicui Wu,Meng Wang,Yunming Fang

The productive motivation of high-energy-density fuels from sustainable feedstocks has been prompted by environmental concerns and resource scarcities. To address this demand, here, the energy-rich C10 cycloalkanes were first afforded with biomass-derived 2-cyclopentenone (2CPE). Initially, bio-based 2CPE can be converted to tricyclo-diketones by (2 + 2) cycloaddition under UV irradiation or zeolite catalysis. The UV-light photocatalysis for dimerization of 2CPE to diketol-cycloadducts disclosed outstanding advantages of cost-effectiveness and feasibility than traditional zeolite-catalyzed manner, with a yield of 53.61 % at ambient temperature for 2 h. Despite the potential for high dimer yield (77.28 %) under thermo-catalysis of H-ZSM-5 zeolite, the reaction conditions (120 °C, 18 h) were found to be suboptimal. Subsequently, diketol-cycloadducts were selectively and efficiently hydrodeoxygenated to provide cyclopentane-based hydrocarbons using a Huang-Minlon methodology with a yield of 97.04 %, where the target components were directly distilled during the reaction. Specifically, the as-synthesized C10 cycloalkane mixture originated from 2CPE possess high density of 0.96 g mL −1 , large volumetric heat net of combustion (NHOC) of 40.02 MJ L −1 , along with low freezing point of −49 °C. These properties suggest that the bio-liquid cycloalkanes can be used as a standalone high-energy fuel or as a blending agent to enhance the performance of conventional jet fuels.

研究领域: 生物化学 · 能源科学
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JOURNAL OF ANTIBIOTICS · 2016 ·Vol. 70 ·期 2 ·216-218 · IF 2.173

A new polysubstituted cyclopentene derivative from Streptomyces sp. HS-NF-1046

Gao Mei-yue,Qi Huan,Li Jian-song,Zhang Hui,Zhang Ji,Wang Ji-dong,Xiang Wen-sheng

Accessions GenBank/EMBL/DDBJ AF389344 KX118440

CAS / MDL: 1397-89-3
研究领域: 微生物学 · 天然产物化学
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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2018 · IF 1.712

Selective oxidation of cyclopentene with H2O2 by using H3PW12O40 and TBAB as a phase transfer catalyst

Yaling Luo,Changjun Liu,Hairong Yue,Siyang Tang,Yingming Zhu,Bin Liang

The selective oxidation of cyclopentene by aqueous H 2 O 2 using H 3 PW 12 O 40 and tetrabutyl ammonium bromide (TBAB) as a phase transfer catalyst has been investigated. The results show that the presence of TBAB significantly improved the oxidation selectivity of cyclopentene. The effects of the reaction conditions on the conversion of cyclopentene were investigated in detail. The optimal reaction conditions are as follows: the H 3 PW 12 O 40 to TBAB molar ratio, 1:1–1:3; H 3 PW 12 O 40 to cyclopentene molar ratio, 0.54:100–0.64:100; and molar ratio of H 2 O 2 to cyclopentene, 1.6:1. The conversion reached to 59.8% in 4 h at 35.0 °C, while the selectivity of glutaraldehyde was 38.0% and the selectivity of 1,2-cyclopentanediol was 55.6%. In addition, a route for oxidation of cyclopentene by aqueous H 2 O 2 using a heteropoly acid and quaternary ammonium salt as a phase transfer catalyst was proposed.

CAS / MDL: 12026-57-2
研究领域: 化学工程 · 催化化学
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APPLIED ORGANOMETALLIC CHEMISTRY · 2025 ·Vol. 39 ·期 6 ·e70172 · IF 0

Selective Oxidation of Cyclopentene Over Amphiphilic Heteropolyacid Catalysts Loaded on Modified Activated Carbon

Xueying Liu,Jiahao Li,Bing Yuan,Fengli Yu

The synthesis of glutaraldehyde and 1,2-cyclopentanediol has great industrial significance. However, the highly selective synthesis of these two compounds, and particularly of glutaraldehyde, is challenging. To improve the reaction rate and product selectivity of cyclopentene oxidation using green hydrogen peroxide (H 2 O 2 , 30 wt%) as an oxidant, activated carbon (AC)-supported amphiphilic vanadium-doped heteropolyacid (HPA) catalysts (AC-COIMI-C n -HPA) were prepared by a series of modifications of AC, including acidification, imidazolylation, ammonium saltification, and HPAs loading. The structures and physicochemical properties of the catalysts were characterized by Fourier infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and nitrogen adsorption–desorption. The developed catalyst exhibits excellent catalytic properties and high selectivity toward glutaraldehyde. The AC carrier increases the number of effective active sites on the catalyst. The amphiphilicity of the catalyst increased the reaction rate. Vanadium doping of HPA enables fine-tuning of the oxidizability of the catalyst. The effects of the different active components of the catalyst, alkyl groups on the imidazole ring, solvent type and dosage, HPA loading on the catalyst, catalyst dosage, oxidant dosage, reaction temperature, and reaction time on the oxidation of cyclopentene were comprehensively examined. Finally, the optimized conditions were determined as follows: HPA doping by four V atoms (PW 8 V 4 ), octyl (C 8 ) linked to the imidazole, 1 mL of acetonitrile, HPA loading of 35 wt%, 500 mg of the catalyst (AC-COIMI-C 8 –35%PW 8 V 4 ), n(H 2 O 2 ):n (cyclopentene) = 2, reaction temperature and time of 40°C and 6 h, respectively. The conversion of cyclopentene was 98.8% and the total selectivity for glutaraldehyde and 1,2-cyclopentanediol was 91.6% (65.2% for glutaraldehyde and 26.4% for 1,2-cyclopentanediol). The catalyst was reused by centrifugation, and high cyclopentene conversion was maintained after three cycles.

CAS / MDL: 10039-32-4 75-05-8
研究领域: 化学工程 · 催化科学
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GREEN CHEMISTRY · 2020 ·Vol. 22 ·期 8 ·2549-2557 · IF 9.48

Double-metal cyanide as an acid and hydrogenation catalyst for the highly selective ring-rearrangement of biomass-derived furfuryl alcohol to cyclopentenone compounds

Xiang Li,Qiang Deng,Lian Yu,Rui Gao,Zhikun Tong,Chenxi Lu,Jun Wang,Zheling Zeng,Ji-Jun Zou,Shuguang Deng

Herein, novel green synthetic routes to 4-hydroxy-2-cyclopentenone (HCP) and 2-cyclopentenone (CPE) from biomass-derived furfuryl alcohol via double-metal cyanide catalysis are proposed. For the synthesis of HCP, in comparison to conventional solid acids (i.e., Amberlyst-15), MOFs with coordinatively unsaturated metal ions as pure Lewis acid sites exhibit advantageous catalytic selectivity in the reaction under an N2 atmosphere in a bi-phasic water/n-hexane solvent system. FeZn and FeZn-P result in an HCP yield of 77.4% and 88.2%, respectively. For the CPE synthesis, the reaction conditions are the same as those for HCP, except a mono-phasic water solvent system and H2 atmosphere were employed. In addition to the acid-catalyzed rearrangement reaction, FeZn-DMC exhibits catalytic hydrogenation capability via heterolytic cleavage of the H–H bond over Zn–N frustrated Lewis pairs, and a CPE yield of 61.5% is obtained. The DFT simulation indicates that the acid sites and catalytic acid sites are ascribed to the tri-coordinatively unsaturated Zn2+ site (Zn(N)3) on the catalyst surface. Moreover, the DMC catalyst shows excellent stability and recycling performance. This work not only provides an efficient and green catalytic system for CPE and HCP preparation but also demonstrates the interesting bifunctional catalysis of both acid and hydrogenation catalysis over DMC.

研究领域: 化学工程 · 生物质能 · 催化化学
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Reaction Chemistry & Engineering · 2025 · IF 3.1

Chemistry of catalytic cracking of cyclohexene and 1-methylcyclopentene

Xueqian Zhang,Jiasong Yan,Shuai Yuan,Shanqing Yu,Qingyu Liu,Xikai Wang,Rui Li

Whether cycloalkanes undergo six- or five-membered ring-opening reaction pathways remains controversial. In this work, the catalytic cracking reactions of cyclohexene and 1-methylcyclopentene, as model compounds, were investigated in a pulse microreactor. The characteristics of the reactions of the two model compounds were compared in terms of isomerization, cracking, and hydrogen transfer reaction, and the reasons for the differences in their catalytic reactions were analyzed in combination with thermodynamic and molecular simulation calculations. The results have shown that the catalytic cracking product distributions of cyclohexene and 1-methylcyclopentene were similar owing to their easy mutual isomerization; the five-membered ring-opening cracking pathway was more thermodynamically advantageous than that of six-membered ring-opening cracking, and therefore, the yield of the ring-opening cracking product of 1-methylcyclopentene was comparatively higher; the main products of the hydrogen transfer reaction of the two compounds were alkanes and aromatic hydrocarbons. By comparing the product distributions and reaction activation energies, the ring-opening reaction pathways were clarified, and the catalytic cracking reaction networks of cyclohexene and 1-methylcyclopentene were established.

CAS / MDL: 693-89-0
研究领域: 化学 · 催化反应
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JOURNAL OF PHYSICAL ORGANIC CHEMISTRY · 2016 ·Vol. 30 ·期 1 ·e3584 · IF 1.515

Design, syntheses and photochromic properties of dithienylcyclopentene optical molecular switches

Chuanming Yu,Bingcheng Hu,Cheng Liu,Jiting Li

A kind of basal diarylethene through an easy synthetic procedure was synthesized and characterized, and a Suzuki coupling reaction was frequently operated to obtain the diarylethenes derivatives with some vivid functional groups like bromo, amido and pyridine. Two methods for derivatives of these switches contain porphyrins were described. All of their spectroscopic and photochromic properties were studied and intercompared. It is indicated that the difference in electron densities of the π-conjugated system of the closed forms has effects upon the absorption maxima in visible region of UV–Vis spectra. Dithienylcyclopentenes linked to porphyrins could emit luminescence substantially that display potentials to be used in the applications of nondestructive readout upon binary data storage and smart materials.

研究领域: 有机化学 · 材料科学 · 光化学
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Nanomaterials · 2018 ·Vol. 8 ·期 10 ·781 · IF 3.504

Modification Effects of B2O3 on The Structure and Catalytic Activity of WO3-UiO-66 Catalyst

Xinli Yang,Nan Wu,Yongxia Miao,Haobo Li

Tungsten oxide (WO3) and boron oxide (B2O3) were irreversibly encapsulated into the nanocages of the Zr-based metal organic framework UiO-66, affording a hybrid material B2O3-WO3/UiO-66 by a simple microwave-assisted deposition method. The novel B2O3-WO3/UiO-66 material was systematically characterized by X-ray diffraction, Fourier transform infrared spectroscopy, N2adsorption, ultraviolet–visible diffuse reflectance spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray phosphorescence, and Fourier transform infrared (FTIR)-CO adsorption methods. It was found that WO3and B2O3were highly dispersed in the nanocages of UiO-66, and the morphology and crystal structure of UiO-66 were well preserved. The B2O3species are wrapped by WO3species, thus increasing the polymeric degree of the WO3species, which are mainly located in low-condensed oligomeric environments. Moreover, when compared with WO3/UiO-66, the B2O3-WO3/UiO-66 material has a little weaker acidity, which decreased by 10% upon the B2O3introduction. The as-obtained novel material exhibits higher catalytic performance in the cyclopentene selective oxidation to glutaraldehyde than WO3/UiO-66. The high catalytic performance was attributed to a proper amount of B2O3and WO3with an appropriate acidity, their high dispersion, and the synergistic effects between them. In addition, these oxide species hardly leached in the reaction solution, endowing the catalyst with a good stability. The catalyst could be used for six reaction cycles without an obvious loss of catalytic activity.Keywords:UiO-66;WO3;B2O3;metal organic frameworks;cyclopentene;glutaraldehyde

研究领域: 材料科学 · 催化化学
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GREEN CHEMISTRY · 2016 ·Vol. 18 ·期 10 ·3075-3081 · IF 8.506

Production of 2,5-hexanedione and 3-methyl-2-cyclopenten-1-one from 5-hydroxymethylfurfural

Dezhang Ren,Zhiyuan Song,Lu Li,Yunjie Liu,Fangming Jin,Zhibao Huo

A novel approach for the production of 2,5-hexanedione (HDN) and 3-methyl-2-cyclopenten-1-one (3-MCO) from 5-hydroxymethylfurfural (HMF) by water splitting with Zn is reported for the first time. The use of high temperature water (HTW) conditions is the key for the efficient conversion of HMF to HDN and 3-MCO. Parameters regarding the Zn amount, temperature and reaction time are optimized and HDN and 3-MCO are produced in 27.3% and 30.5% yields, respectively. The roles of HTW and ZnO obtained by oxidation of Zn in water for the conversion of HMF, together with intermediate structures, are discussed to understand the mechanism of the reaction.

研究领域: 化学工程 · 有机化学
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JOURNAL OF MATERIALS SCIENCE · 2019 ·Vol. 54 ·期 9 ·6853-6866 · IF 3.442

Immobilization of tungsten chelate complexes on functionalized mesoporous silica SBA-15 as heterogeneous catalysts for oxidation of cyclopentene

Jin Manman,Guo Zhenmei,Lv Zhiguo

An efficient hybrid mesoporous heterogeneous catalyst system was synthesized via covalently grafting tungsten chelate complex W- N , N ( N , N  = (3-triethoxysilylpropyl) [3-(2-pyridyl)-1-pyrazolyl] acetamide, N,N -chelating ligand) in organic moieties (diphenyldichlorosilane, DPHS)-functionalized mesoporous silica SBA-15 or pure SBA-15. Characterization of synthesized materials via N 2 sorption, XRD, TEM, UV–Vis DRS, 29 Si MAS NMR, element analysis, and FT-IR indicated that W- N , N was successfully anchored and highly dispersed in the mesochannels of SBA-15 and the mesostructure of SBA-15 was maintained during the grafting course. The synthesized hybrid catalysts were highly active and authentically heterogeneous in triphasic oxidation reaction of cyclopentene (CPE) with H 2 O 2 . W, N - N immobilized on functionalized SBA-15 with DPHS moieties (W- N , N -DPHS-SBA-15) showed better catalytic properties (activity and stability) than its unmodified counterpart W- N , N -SBA-15 catalyst. Besides, possible catalytic reaction route for CPE oxidation with H 2 O 2 over W- N , N -DPHS-SBA-15 catalyst was proposed. The amphiphilic mesochannels of W- N , N -DPHS-SBA-15 provided suitable accommodation for both hydrophilic H 2 O 2 and hydrophobic CPE molecules and acted as nanoreactors for CPE/H 2 O 2 /solid triphase reaction.

研究领域: 催化化学 · 材料科学
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Processes · 2025 ·Vol. 13 ·期 5 ·1435 · IF 2.8

Development of a Computer-Aided Process for Recovering and Purifying 2-Methyl-2-Cyclopentenone Based on Measured Phase Equilibrium Data

Zhongfeng Geng,Yunfei Bai,Ke Zhang,Feng Shi

2-Methyl-2-cyclopentenone (MCP) is the main by-product of the newly developed heterogeneous catalysis process for producing crotonaldehyde, which serves as an important intermediate for drug synthesis. However, how to recover and purify MCP from the product mixture is not known. To decipher this, a computer-aided process based on the measured phase-equilibrium data was developed. The improved Rose–Williams equilibrium kettle was used to measure the vapor–liquid equilibrium data for MCP–crotonaldehyde and MCP–water. Surprisingly, MCP and water formed a minimum azeotrope, which aided its own recovery from its dilute solution. The mole fraction of MCP in the azeotrope was 9.1%, the mole fraction of water was 90.9%, and the azeotropic temperature was 96.8 °C. Equilibrium data from the two binary systems were correlated using the Wilson and NRTL activity coefficient models. The NRTL-RK model was selected to simulate the process for recovering and purifying MCP. A two-column process was developed and optimized in this study, and the aim of effectively utilizing the by-product MCP was achieved with this process.

研究领域: 化学工程 · 药物合成
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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2022 · IF 3.898

Lacunary silicotungstic heteropoly salts as high-performance catalysts in oxidation of cyclopentene

Peiyin Chen,Yanxiong Fang,Kaihong Xie,Yao Chen,Yang Liu,Hongliang Zuo,Weijian Lu,Baoyu Liu

The development of polyoxometalates for olefin oxidation is critical to achieving the green chemical process of the C5 fraction further processing. Di-lacunary silicotungstic anions were easily obtained by continuously adjusting the pH instead of the traditional step-by-step method, which exhibited excellent performance in the catalytic oxidation of cyclopentene (CPE) to aldehydes or alcohols. The 93.69% CPE conversion and 97.15% total product selectivity (41.38% for glutaraldehyde (GA) and 55.77% for 1,2-cyclopentanediol (1,2-diol) were achieved by using H 2 O 2 as the oxidant and acetonitrile as the solvent. Through complementary characterization, it was found that the optimized di-lacunary silicotungstic polyoxometalate retained a complete Keggin structure, and exhibited better catalytic activity and stability than the mono-lacunary or saturated silicodecatungstate because it exposed more catalytic active centers. Furthermore, in situ FT-IR spectra was utilized to monitor the reaction process, revealing the formation of the active species W(O 2 ) on the di-lacunary silicotungstic polyoxometalate and the intermediate epoxycyclopentane during the catalytic oxidation of cyclopentene.

研究领域: 化学工程 · 催化材料科学
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