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Journal of Nanomaterials · 2015 · IF 1.644

Synthesis of Renewable Energy Materials, Sodium Aluminum Hydride by Grignard Reagent of Al

Jun-qin Wang,Jian-feng Gao,Zhi-gang Wu,Guo-li Ou,Yu Wang

The research on hydrogen generation and application has attracted widespread attention around the world. This paper is to demonstrate that sodium aluminum hydride can be synthesized under simple and mild reaction condition. Being activated through organics, aluminum powder reacts with hydrogen and sodium hydride to produce sodium aluminum hydride under atmospheric pressure. The properties and composition of the sample were characterized by FTIR, XRD, SEM, and so forth. The results showed that the product through this synthesis method is sodium aluminum hydride, and it has higher purity, perfect crystal character, better stability, and good hydrogen storage property. The reaction mechanism is also discussed in detail.

CAS / MDL: 7646-69-7
研究领域: 材料科学 · 能源化学
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International Journal of Chemical Engineering · 2022 · IF 2.729

Thermal Hazards of Synthesizing a Grignard Reagent under Different Dosing Rates

Wei Wang,Jiancun Gao,Chenguang Shi,Shengnan Wang,Yujing Li,Xiong Dai,Tianmeng Jiang

Thermal safety during the synthesis of a Grignard reagent under different dosing rates was evaluated in this work. A reaction calorimeter (SIMULAR) was used to investigate the heat release under isothermal experiment in the range of 0.5–2.0 g⋅min−1 dosing rates. The thermal decomposition of the Grignard reagent was analyzed using accelerating rate calorimetry (ARC). Furthermore, the risk assessment of thermal runaway was analyzed using a risk matrix and a Stoessel criticality diagram. The results indicate that decreasing the dosing rate can decrease the risk level of synthesizing the Grignard reagent from class 3 to class 1. However, the risk level was class 3 at different dosing rates when the induction period was considered. In the case of cooling failure, the most hazardous moment was the induction period, followed by the dosing period. These findings provide further evidence that the dose rate of 0.5 g⋅min−1 was safer to produce Grignard reagents.

研究领域: 化学工程 · 安全科学 · 物理化学
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TETRAHEDRON · 2015 · IF 2.641

Nickel-catalyzed cross-coupling of sterically hindered 1-bromomethyl-o-carborane with alkyl and aryl Grignard reagents

Juyou Lu,Hong Wan,Yunna Xue,Yongmei Du,Jian Lu

A convenient and efficient Ni-catalyzed reaction has been developed for synthesis of mono-substituted o -carboranes, involving cross-coupling of readily available and sterically hindered 1-bromomethyl- o -carborane with various alkyl and aryl Grignard reagents under mild conditions, and the corresponding o -carborane derivatives were obtained in good to excellent yields. This method should provide a new strategy for construction of diverse and useful functionalized boron cluster compounds for medicinal chemistry and material chemistry.

研究领域: 有机化学 · 材料化学 · 药物化学
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PROCESS SAFETY AND ENVIRONMENTAL PROTECTION · 2021 · IF 6.158

Process hazard evaluation and exothermic mechanism for the synthesis of n-butylmagnesium bromide Grignard reagent in different solvents

Zhen Cheng,Lei Ni,Junjie Wang,Juncheng Jiang,Hang Yao,Qiang Chen,Fusheng Cui,Wei Jiang,Shuliang Ye

The synthesis of Grignard reagents, which are formed by the reaction of magnesium and organic halides (RX), is hazardous because of the highly exothermic nature of this reaction. In this work, calorimetry and infrared (IR) spectroscopy were used to identify the exothermic mechanism and process hazards for the synthesis of n -butylmagnesium bromide Grignard reagent ( n -BuMgBr) in diethyl ether (DE), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), cyclopentylmethyl ether (CPME), and diethylene glycol butyl ether (DGBE). The latter three solvents were chosen by the substitution principle of the “inherent safety” design concept, which aims to reduce the risk of the target reaction in a fundamental manner. An EasyMax102 calorimeter was used to characterize the exothermic behavior of the reactions using isothermal and isoperibolic experiments carried out in a semi-batch glass reactor coupled with an IR probe to monitor changes in the species and concentrations during the reaction process. An adiabatic TAC-500A calorimeter was also used to understand the adiabatic decomposition behavior of the products obtained in the isothermal experiments under the worst-case (cooling failure and thermal runaway) scenario. Meanwhile, density functional theory calculations were performed to understand the reaction pathway and associated energies based on the experimental data. Further, the risk assessment of thermal runaway was analyzed using a risk matrix and a Stoessel criticality diagram. The results indicate that the risk of the reactions when using 2-MeTHF, CPME, and DGBE are all class 1, making reactions in these solvents inherently safer than those using DE or THF, which were both class-3 risks. These findings provide further evidence that 2-MeTHF, CPME, and DGBE are safer than the typical solvents used for the industrial production of Grignard reagents.

CAS / MDL: 5614-37-9 96-47-9
研究领域: 化学工程 · 安全科学 · 理论化学
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Chemistry-An Asian Journal · 2015 ·Vol. 10 ·期 4 ·844-848 · IF 4.587

Copper-Catalyzed Enantioselective Conjugate Addition of Grignard Reagents to Methyl 4,4,4-Trifluorocrotonate: Synthesis of Enantioenriched Trifluoromethylated Compounds

Li-Ying Zhang,Jia-Hui Zhou,Yun-He Xu,Teck-Peng Loh

Graphical Someone please conjugate this : Copper-catalyzed enantioselective 1,4-conjugate addition of methyl 4,4,4-trifluorocrotonate with aliphatic Grignard reagents to access asymmetric tertiary carbon center attached with a trifluoromethyl group was achieved under mild reaction condition. The desired products could be obtained in reasonable yields and good enantioselectivities. Copper-catalyzed enantioselective 1,4-conjugate addition of methyl 4,4,4-trifluorocrotonate with aliphatic Grignard reagents to access an asymmetric tertiary carbon center attached with a trifluoromethyl group was achieved under mild reaction conditions. The desired products could be obtained in reasonable yields and good enantioselectivities.

研究领域: 有机化学 · 合成化学
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