JOURNAL OF CHEMICAL RESEARCH
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2023
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IF 1.4
Ruilong Jia,Qizhuozhuo Hua,Xiaonan Ma,Guangfu Liao
Allyl alcohol and water can form the lowest boiling point azeotrope, but it is very hard to acquire high-purity allyl alcohol by normal distillation methods. Herein, a separation and purification protocol is developed for perfectly separating an azeotropic mixture of allyl alcohol and water using the salting-out method, in which three potassium phosphate salts, K5P3O10, K3PO4, and K4P2O7, are systematically investigated as salting-out agents, and finally a product consisting of > 99% allyl alcohol is obtained. A thermodynamic study demonstrates that this process involves endothermy and increment entropy. There is a good correlation between the solubility of allyl alcohol and the molar concentration of salt (mol per 1 kg water), and the solubility of the allyl alcohol in the organic phase or the water phase can be forecast using the mass percentage of salts. This work provides a new methodology for the efficient separation of an azeotropic mixture of allyl alcohol and water.
研究领域:
化学工程
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物理化学
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产品关联
DOI
高影响因子
MONATSHEFTE FUR CHEMIE
·
2023
·Vol. 154
·期 10
·1189-1195
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IF 1.8
Wang Peng,Shi Huibing,Feng Baolin,Zhao Deming,Wu Haigang
The Ru-catalyzed highly selective alkoxycarbonylation of allenes with aliphatic alcohols (also as solvent) allow to produce useful α , β -unsaturated esters in good to excellent yields at 70 °C. Efficient regioselectivity could be controlled in the presence of N-ligands while the P-ligands had no influence on the conversion of substrates and the chemo/regioselectivity of target products. By involving N-ligand 4,7-dimethyl-1,10-phenanthroline in the catalytic system, α , β -unsaturated esters were obtained with high conversion and chemo/regioselectivity (conversion up to 99%, chemical selectivity up to 99%, regioselectivity of branched ester/linear ester up to 89/11). Graphical abstract
研究领域:
有机化学
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催化化学
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DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2025
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IF 3.9
Alfin Kurniawan,Jian Qiang Zhong,Ze Zhen Wang,Chun Hui Zhou
Allyl alcohol, an industrially valuable intermediate in organic synthesis, is conventionally produced through selective hydrogenation of acrolein and hydrolysis of chloropropene. However, these processes currently face challenges due to the unsustainability of fossil feedstocks. A more sustainable production of allyl alcohol from renewable feedstock (i.e., glycerol) has been demonstrated through gas-phase catalytic reaction over metal oxide catalysts with and without external H2. Improved understanding of the reaction mechanism of glycerol to allyl alcohol conversion is an important effort to rationally design more efficient catalysts. In this work, we investigate gas-phase conversion of glycerol to allyl alcohol through consecutive dehydration and hydrogen transfer reactions over Mo–V oxides supported on acid-modified montmorillonite (HMMT). The use of HMMT as a support enables the well dispersion of metal oxide particles with nominal loadings up to 5 wt % on the catalyst surface while the acidic sites facilitate dehydration of glycerol to acrolein with ∼74% selectivity. By modulating the nominal total Mo+V loading, Mo–V/HMMT catalyst with a 10 wt % metal loading afforded allyl alcohol in 22% yield at 320 °C and ambient pressure. X-ray photoelectron spectroscopic analysis of this bifunctional catalyst in the as-prepared and post-catalysis (spent) states showed changes in the surface Mo(VI)═O species and V4+/V5+ redox ratio; the latter was found to decrease due to the involvement of lower valence V4+ species in the hydrogen transfer reaction of acrolein. Meanwhile, the amount of surface Mo(VI)═O species with weak electronic metal–support interaction decreases after the reaction. Catalytic tests using an aqueous acrolein feed solution suggested the role of water as a hydride donor in transfer hydrogenation of this unsaturated aldehyde to allyl alcohol, while the addition of alcohol-containing compounds, such as 2-propanol and 1,2-propanediol leads to lower allyl alcohol selectivity with time on stream. The results presented here could guide the development of improved supported Mo−V oxide catalysts and reaction systems for efficient gas-phase glycerol conversion to allyl alcohol.
研究领域:
化学工程
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催化科学
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DOI
高影响因子
ADVANCED SYNTHESIS & CATALYSIS
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2021
·Vol. 363
·期 6
·1672-1684
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IF 5.837
Zhipeng Liu,Xinwei Hu,Can Yang,Haisheng Xie,Huanfeng Jiang,Wei Zeng
Graphical A Rh(III)-catalyzed C sp 2 −C sp 3 bond cleavage/carbonylethylation of α-indolyl alcohols with allylic alcohols has been reported. This transformation involved a cascade C−C bond cleavage/C−C bond formation, and provides a novel approach to assemble 2-carbonylethylindole skeletons.
研究领域:
有机化学
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催化反应
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DOI
高影响因子
Asian Journal of Organic Chemistry
·
2017
·Vol. 7
·期 1
·240-247
·
IF 2.788
Rui Yan,Zhong-Xia Wang
Graphical Oxidative coupling of allylic alcohols : [Cp*RhCl 2 ] 2 was demonstrated to catalyze the oxidative coupling of alkenylpyridines with allylic alcohols through alkenyl C−H activation in the presence of AgOTf and AgOAc to afford β-alkenyl ketones and aldehydes in moderate to good yields. [Cp*RhCl 2 ] 2 was demonstrated to catalyze the oxidative coupling of alkenylpyridines with allylic alcohols through alkenyl C−H activation in the presence of AgOTf and AgOAc to afford β-alkenyl ketones and aldehydes in moderate to good yields. Allylic alcohol, 1-aryl and 1-alkyl allylic alcohols can be coupled with various alkenylpyridines. The reaction occurred at the γ-position of allylic alcohols and the cis -β-position of the alkenylpyridines.
研究领域:
有机化学
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催化化学
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DOI
高影响因子
RESEARCH ON CHEMICAL INTERMEDIATES
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2012
·Vol. 39
·期 3
·869-874
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IF 0.697
Dong Shuangjian,Li Yunling,Li Qiuxiao
The synthesis of unsaturated tertiary amine by the amination of oleyl alcohol and dimethylamine under atmospheric pressure over Cu–Ni catalysts supported on CaCO 3 was studied. The yield of tertiary amine and the retention rate of the unsaturated bond can reach 95.4 and 93.3 %, respectively. The yields of tertiary amine over different Cu/Ni ratios catalysts were close to each other, which meant that Cu/Ni ratios had no obvious influence on the production of tertiary amine, while the retention rate of the unsaturated bond over the catalyst containing only Cu was higher than the catalysts containing Cu–Ni. The major effect of the Cu element was dehydrogenation, and the ability of the hydrogenation was weak. The ability of the Ni element to break the carbon–carbon bonds and hydrogenation was strong. Therefore, the performance of the Cu catalyst was better than the conventional Cu–Ni-based catalyst for the retention of the unsaturated bond in long-chain R of the tertiary amine.
研究领域:
化学工程
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催化化学
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产品关联
DOI
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
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2022
·
IF 9.221
Qianchun Zhang,Yuxian Zhao,Xuan Shang,Shan Tang,Li Jiang,Yun Wu,Qin Zhou,Shiqin Li
Methallyl alcohol (MA), which is a common volatile organic compound, in vapor form can cause respiratory irritation, headache, nausea, and vomiting. Therefore, the development of a highly selective, excellently sensitive, and efficient sensor for rapidly identifying trace MA is essential. In this study, a La 2 O 3 /α-Al 2 O 3 composite with excellent cataluminescence (CTL) activity in the presence of MA was successfully synthesized. The CTL sensor based on as-prepared La 2 O 3 /α-Al 2 O 3 exhibited high selectivity for MA vapor as well as response and recovery times of 1 and 6 s, respectively. Under the optimal conditions for MA detection, the La 2 O 3 /α-Al 2 O 3 sensor exhibited a linear range of 0.0025–0.50 mg/L (correlation coefficient, R 2 = 0.998) and a low limit of detection of 0.61 μg/L at a signal-to-noise ( S/N ) = 3. The La 2 O 3 /α-Al 2 O 3 sensor was also used to determine the MA content in spiked samples and volatile gases generated from a medicine cabinet. Excellent recoveries in the range of 82.5–107% were obtained, with a corresponding relative standard deviation ( n = 5) in the range of 2.1–4.7%. Furthermore, the CTL sensing mechanism was investigated through density functional theory and high-performance liquid chromatography-ultraviolet analyses.
研究领域:
环境科学
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材料科学
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分析化学
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DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
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2025
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IF 3.6
Mengxuan Bai,Xuetong Zhang,Shengxin Zhang,Caicai Zhang,Zhiqiang Hao,Jin Lin
γ-Amino alcohol is of great importance, as a broad number of bioactive and pharmaceutical alcohols contain this motif. Herein, a selective formal anti-Markovnikov hydroamination of allyl alcohols to access γ-amino alcohols has been achieved by using NNN-pincer Ru complexes. The electronic effect of the catalysts is critical for their catalytic performance. A wide substrate scope (65 examples) and up to 96% yields were achieved at low catalyst loadings via a borrowing hydrogen (BH) process in one pot. This protocol was easily extended to the hydroamination of both primary and secondary allyl alcohols and applications for the synthesis of drug derivatives.
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DOI
PubMed
高影响因子
ChemSusChem
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2017
·Vol. 10
·期 23
·4715-4724
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IF 7.226
Wenda Hu,Yan Wan,Lili Zhu,Xiaojie Cheng,Shaolong Wan,Jingdong Lin,Yong Wang
Graphical Mal to Mol and Dal ! Methylallyl alcohol and diethyl acetal are synthesized from methacrolein by using different Sn-modified Beta zeolites (Sn-β) as catalysts. The Sn-β precalcined in Ar followed by sodium-exchange exhibited the highest selectivity toward the desired products. The possible reaction pathways of the reaction between α,β-unsaturated aldehydes and primary alcohols were investigated and proposed. A new strategy was developed to simultaneously produce two important chemicals, namely, methallyl alcohol (Mol) and diethyl acetal (Dal) from methacrolein in ethanol solvent at low temperature with the use of Beta zeolites modified by tin (Sn-β catalysts). All the Sn-β catalysts were prepared by the solid-state ion-exchange method, wherein the calcination step was conducted under different gas atmospheres. The catalyst precalcined in Ar (Sn-β-Ar) had a reduced number of extra-framework Sn species and enabled more Sn species to be exchanged into the framework as isolated tetrahedral Sn IV , enhancing the catalytic activity of the Meerwein–Ponndorf–Verley (MPV) reaction. The sodium-exchanged Sn-β-Ar, with a reduced number of weak Brønsted acid sites, led to an even better selectivity for Mol, owing to the restriction of the side reactions such as acetalization, addition, and etherification. Under optimized catalyst and reaction conditions, the yield of Mol and Dal reached approximately 90 % and 96 %, respectively. The possible reaction pathways, along with a complex network of side products, was proposed after a detailed investigation through the use of different substrates as reactants. The fine-tuning of Sn-β catalysts through different treatments discussed in this work is of great significance toward the understanding and manipulation of complex reactions between α,β-unsaturated aldehydes and primary alcohols.
研究领域:
化学工程
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催化科学
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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING SCIENCE
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2023
·
IF 4.7
Jiale Wu,Yuan Tao,Dang Cheng,Fener Chen
Herein, we demonstrate a hybrid microflow system consisting of a coaxial double-tube microreactor and a capillary microreactor for performing borohydride reduction of α , β -unsaturated esters to allylic alcohols in a highly controlled and safe manner. Using methyl cinnamate as the model substrate and LiBH 4 as reductant, complete conversion was achieved in 75 s residence time at 80 ℃ with up to 85% yield of the target product cinnamyl alcohol under optimized conditions in the hybrid microflow system, enabling selective borohydride reduction of α , β -unsaturated esters to allylic alcohols without the need of using metallic salts as additives or co-reagents. The kinetics of this reduction reaction has been examined and modelled, providing an understanding of the intensified reaction behaviour and the reaction performance of the hybrid microflow process. The results presented can shed new light on the development of continuous microflow processes for the hydridic type of reductions.
研究领域:
化学工程
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有机合成
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产品关联
DOI
高影响因子
Nature Communications
·
2013
·Vol. 4
·期 1
·1-7
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IF 10.015
Tang Xinjun,Zhu Can,Cao Tao,Kuang Jingqiang,Lin Weilong,Ni Shengjun,Zhang Jiasheng,Ma Shengming
Allenes are important building blocks in organic synthesis and have attracted much attention from researchers worldwide. So far, mono- and 1,3-disubstituted allenes can be prepared easily by applying the allenylation of terminal alkynes reaction of aldehydes. However, trisubstituted allenes have never been reported using this reaction due to the extremely low reactivity of ketones. Here, we report the one-pot synthesis of trisubstituted allenes from terminal alkynes and ketones utilizing cadmium iodide as the mediator. With this protocol, a series of different allenes, including 1,5-bisallenes and optically active allenols, which are especially important in synthetic chemistry, have been successfully prepared.
研究领域:
有机化学
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合成化学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
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2024
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IF 6.5
Liru Song,Wenyu Wang,Jun Tang,Xu Guo,Xiantai Zhou,Qingping Ke
Selective aerobic epoxidation of allylic alcohols and olefins presents a promising solution to the modern chemical industry. However, the development of non-noble metal catalysts with superior catalytic performance for this reaction remains a significant challenge. This study introduces a plasmonic photothermal-catalytic system centered around nano LaSrCoNiO 6 (LSCNi-N) catalyst, enabling the epoxidation of cinnamyl alcohol and styrene mediated by LSPR effect under visible light illumination (>420 nm). This catalyst exhibits superior epoxidation catalytic performance, with selectivities of up to 72.3 % in a 93.4 % conversion of cinnamyl alcohol and 91.8 % selectivity of styrene oxide at almost 100 % conversion of styrene. Mechanistic studies reveal that the high selectivity derives from the in-situ photochemical formation of H 2 O 2 mediated by the localized surface plasmon resonance effect of LSCNi-N and hole scavenger effect of cinnamyl alcohol. These findings highlight the potential of designing plasmonic transition-metal oxidic catalysts to overcome challenges in selectively synthesizing fine chemicals through visible light catalysis.
研究领域:
化学工程
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材料科学
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环境化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）