Climent Maria J, Corma Avelino, Iborra Sara, Martí Laura
Instituto de Tecnología Química (UPV-CSIC), Universitat Politécnica de València, Avda dels Tarongers s/n, 46022, Valencia (Spain), Fax: (+34) 963877809.
ChemSusChem. 2014 Apr;7(4):1177-85. doi: 10.1002/cssc.201301064. Epub 2014 Mar 11.
1,5-Benzothiazepines derivatives were obtained first by starting from 1,3-diphenylpropenone derivatives (chalcones) and 2-aminothiophenol by using aluminosilicate solid catalysts. However, diffusional limitations and the strong adsorption of products on the catalyst are deleterious for catalyst activity and life. Then a structured amorphous mesoporous catalyst with large pores and mild acidity that works at higher temperatures allowed us to obtain high conversions (99 %) and selectivities (98 %) of the desired product. A one-pot synthesis of 1,5-benzothiazepines that starts from benzaldehyde, acetophenone, and 2-aminothiophenol with 95 % yield was performed by combining optimized solid base and acid catalysts in batch mode as well as in a continuous-flow reactor system. Much better conversion and selectivity as well as process intensification has been achieved with the structured mesoporous materials by avoiding intermediate and final neutralization and purification steps required in the synthesis reported previously that uses homogeneous catalysts.
1,5-苯并硫氮杂䓬衍生物最初是通过使用硅铝酸盐固体催化剂,以1,3-二苯基丙烯酮衍生物(查耳酮)和2-氨基硫酚为原料制得的。然而,扩散限制以及产物在催化剂上的强烈吸附对催化剂活性和寿命是有害的。随后,一种具有大孔和适度酸度、能在较高温度下工作的结构化无定形介孔催化剂使我们能够获得所需产物的高转化率(99%)和高选择性(98%)。通过在间歇模式以及连续流反应器系统中结合优化的固体碱和酸催化剂,从苯甲醛、苯乙酮和2-氨基硫酚出发,以95%的产率进行了1,5-苯并硫氮杂䓬的一锅法合成。通过避免先前报道的使用均相催化剂的合成中所需的中间和最终中和及纯化步骤,结构化介孔材料实现了更好的转化率、选择性以及过程强化。