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- ItemContinuous Flow Synthesis of Azoxybenzenes by Reductive Dimerization of Nitrosobenzenes with Gel‐Bound Catalysts(Weinheim : Wiley-VCH Verl., 2021) Schmiegel, Carsten J.; Berg, Patrik; Obst, Franziska; Schoch, Roland; Appelhans, Dietmar; Kuckling, DirkIn the search for a new synthetic pathway for azoxybenzenes with different substitution patterns, an approach using a microfluidic reactor with gel-bound proline organocatalysts under continuous flow is presented. Herein the formation of differently substituted azoxybezenes by reductive dimerization of nitrosobenzenes within minutes at mild conditions in good to almost quantitative yields is described. The conversion within the microfluidic reactor is analyzed and used for optimizing and validating different parameters. The effects of the different functionalities on conversion, yield, and reaction times are analyzed in detail by NMR. The applicability of this reductive dimerization is demonstrated for a wide range of differently substituted nitrosobenzenes. The effects of these different functionalities on the structure of the obtained azoxyarenes are analyzed in detail by NMR and single-crystal X-ray diffraction. Based on these results, the turnover number and the turnover frequency were determined.
- ItemAir-Stable CpCoI–Phosphite–Fumarate Precatalyst in Cyclization Reactions: Comparing Different Methods of Energy Supply(Weinheim : Wiley-VCH Verl., 2018) Fischer, Fabian; Hapke, MarkoThe robust CoI precatalyst [CpCo(P{OEt}3)(trans-MeO2CHC=CHCO2Me)] was investigated in cyclotrimerizations, furnishing benzenes and pyridines from triynes, diynes and nitriles, comparing the influence of different ways of energy supply; namely, irradiation and conventional (thermal) or microwave heating. The precatalyst was found to work under all conditions, including the possibility to catalyze cyclotrimerizations at room temperature under photochemical conditions at longer reaction times. Performance of the reactions in a microwave reactor proved to be the most time-efficient way to rapidly assemble the expected reaction products; however, careful selection of reaction conditions can be required. The synthesis of pyridines and isoquinolines successfully involved the utilization of versatile functionalized nitriles, affording structurally interesting reaction products. Comparison with the known and often applied precatalyst CpCo(CO)2 demonstrated the significantly higher reactivity of the CpCoI–phosphite–olefin precatalyst.
- ItemHexacyanidosilicates with Functionalized Imidazolium Counterions(Weinheim : Wiley-VCH, 2020) Harloff, Jörg; Laatz, Karoline Charlotte; Lerch, Swantje; Schulz, Axel; Stoer, Philip; Strassner, Thomas; Villinger, AlexanderFunctionalized imidazolium cations were combined with the hexacyanidosilicate anion, [Si(CN)6]2–, by salt metathesis reactions with K2[Si(CN)6], yielding novel ionic compounds of the general formula [R–Ph(nBu)Im]2[Si(CN)6] {R = 2-Me (1), 4-Me (2), 2,4,6-Me = Mes (3), 2-MeO (4), 2,4-F (5), 4-Br (6); Im = imidazolium}. All synthesized imidazolium hexacyanidosilicates decompose upon thermal treatment above 95 °C (96 – 164 °C). Furthermore, the hexa-borane-adduct [Mes(nBu)Im]2{Si[(CN)B(C6F5)3]6}·6CH2Cl2 (7), which is thermally stable up to 215 °C, was obtained from the reaction of 3 with Lewis acidic B(C6F5)3. In CH3CN solution, decomposition of the hexaadduct to the Lewis-acid-base adduct CH3CN–B(C6F5)3 and [(C6F5)3B·(µ-CN)·B(C6F5)3]– was observed. All synthesized compounds were isolated in good yields and were completely characterized including single crystal structure elucidations. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.