9003-49-0Relevant articles and documents
Acid- And base-switched palladium-catalyzed γ-C(sp3)-H alkylation and alkenylation of neopentylamine
Zhang, Jinquan,Zhang, Shuaizhong,Zou, Hongbin
supporting information, p. 3466 - 3471 (2021/05/31)
The functionalization of remote unactivated C(sp3)-H and the reaction selectivity are among the core pursuits for transition-metal catalytic system development. Herein, we report Pd-catalyzed γ-C(sp3)-H-selective alkylation and alkenylation with removable 7-azaindole as a directing group. Acid and base were found to be the decisive regulators for the selective alkylation and alkenylation, respectively, on the same single substrate under otherwise the same reaction conditions. Various acrylates were compatible for the formation of C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds. The alkenylation protocol could be further extended to acrylates with natural product units and α,β-unsaturated ketones. The preliminary synthetic manipulation of the alkylation and alkenylation products demonstrates the potential of this strategy for structurally diverse aliphatic chain extension and functionalization. Mechanistic experimental studies showed that the acidic and basic catalytic transformations shared the same six-membered dimer palladacycle.
Safe production process of butyl acrylate
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Paragraph 0027-0046, (2020/07/15)
The invention relates to a safe production process of butyl acrylate, belonging to the technical field of organic synthesis. According to the invention, acrylic acid is used as an initial raw material; acrylate is prepared firstly; and then the acrylate reacts with bromobutane to synthesize the butyl acrylate. The safe production process has the following beneficial effects: (1) the use of acidicsubstances is avoided, and the corrosion of the acidic substances to pipelines is prevented; (2) reaction temperature is reduced; and (3) rectification separation effect is better, and the separated bromobutane can be repeatedly utilized.
Acrylate Esters by Ethenolysis of Maleate Esters with Ru Metathesis Catalysts: an HTE and a Technoeconomic Study
Copéret, Christophe,De Jesus Silva, Jordan,Engl, Pascal S.,Fedorov, Alexey,Lange, Jean-Paul,Togni, Antonio,Tsygankov, Alexey
, (2020/04/29)
A high throughput experimentation (HTE) study identified active Ru metathesis catalysts and reaction conditions for the ethenolysis of maleate esters to the respective acrylate esters. Catalysts were tested at various loadings (75–10’000 ppm) and temperatures (30–60 °C) with maleate esters dissolved in toluene (up to ca. 44 wt-%) or neat and at variable partial pressures of ethylene (0.2–10 bar). Ruthenium catalysts containing a PCy3 ligand, such as 1st or 2nd generation Grubbs catalysts, as well as the state-of-the-art catalysts containing cyclic alkyl amino carbene (CAAC) ligands, are generally inferior to Hoveyda–Grubbs 2nd generation catalyst in ethenolysis of maleates. Productive turnover numbers could exceed 1900 if the ethenolysis reaction is performed at low ethylene pressure (0.2–3 bar) and reach 5200 when a polymeric phenol additive was used. Such catalytic performance falls well within the window practiced in industry. Moreover, a crude technoeconomic analysis finds similar production cost for the ethenolysis route and conventional technology, that is, propene oxidation followed by esterification, justifying research to further improve the ethenolysis route.
