- Unraveling the cation and anion effects and kinetics for ionic liquid catalyzed direct synthesis of methyl acrylate under mild conditions
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The direct synthesis of methyl acrylate (MA) from methyl acetate and trioxane at 350-380 °C is regarded as a supplementary route for the industrial propylene oxidation process; however, it suffers from rapid catalyst deactivation. Herein, a novel ionic liquid catalyzed mild liquid-phase system was developed for the direct synthesis of MA from methyl acetate and trioxane, where N,O-bis(trimethylsilyl)acetamide (BSA) was used as a probase for α-deprotonation and enol silyl etherification of methyl acetate. The trioxane decomposition to formaldehyde and methyl acetate enolization to 1-methoxy-1-trimethylsilyloxyethene proceeded with the catalysis of [Cation]Cl/MClx (M = Cu+, Fe3+, Zn2+ and Al3+) and [Cation]F, respectively. The cations and anions were observed to have significant effects on the yield and selectivity of MA, owing to the steric hindrance, acid site category and strength confirmed by pyridine probing FT-IR characterization. As a result, up to 60.2% yield with 94.6% selectivity of MA could be achieved when [N3,3,3,3]F and [N3,3,3,3]Cl/AlCl3 with 67 mol% AlCl3 were used in the presence of BSA at 25 °C. Kinetic studies indicated that the trioxane decomposition with the activation barrier of 41.2 ± 0.3 kJ mol-1 was the rate-determining step.
- Wang, Gang,Li, Zengxi,Li, Chunshan,Zhang, Suojiang
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p. 7913 - 7923
(2020/12/01)
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- Synthesis of Quaternary Ammonium Fluoride Salts by a Solid-Liquid Halogen Exchange Process in Protic Solvents
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Both hydrophilic and lipophilic quaternary ammomium fluoride compounds are prepared by direct exchange of the corresponding halides with solid potasium fluoride containing an optimized amount of water (4.0 mol percent).The procedure is most effective when methanol is applied as a solvent.A variety of quaternary ammonium fluorides were prepared in 75-97percent yield.
- Dermeik, Salman,Sasson, Yoel
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p. 4827 - 4829
(2007/10/02)
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- Convenient Procedures for the Preparation of Lipophilic Quaternary Onium Fluorides, Hydrogendifluorides and Dihydrogentrifluorides via Ion Exchange in Two-Phase Systems
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A series of lipophilic quaternary onium fluorides 2, hydrogendifluorides 3, and dihydrogentrifluorides 4 are easily synthesized in almost quantitative yields from the corresponding quaternary hydrogen sulfates by exchange with the appropriate anion in an organic aqueous two-phase system; alternatively quaternary salts 4 can be prepared from onium chlorides 5 or bromides 6 under the same conditions.
- Landini, Dario,Molinari, Henriette,Penso, Michele,Rampoldi, Alessandro
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p. 953 - 955
(2007/10/02)
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