Bankar Digambar B, Hawaldar Ranjit R, Arbuj Sudhir S, Moulavi Mansur H, Shinde Santosh T, Takle Shrikant P, Shinde Manish D, Amalnerkar Dinesh P, Kanade Kaluram G
Centre for Materials for Electronics Technology (C-MET) Panchwati, Off Pashan Road Pune-411008 India
P. G. Department of Chemistry, R. B. Narayanrao Borawake College Shrirampur Ahmednagar-413709 India.
RSC Adv. 2019 Oct 14;9(56):32735-32743. doi: 10.1039/c9ra06693d. eCollection 2019 Oct 10.
One-pot green synthesis of propargylamines using ZnCl loaded TiO nanomaterial under solvent-free conditions has been effectively accomplished. The aromatic aldehydes, amines, and phenylacetylene were reacted at 100 °C in the presence of the resultant catalyst to form propargylamines. The nanocrystalline TiO was initially synthesized by a sol-gel method from titanium(iv) isopropoxide (TTIP) and further subjected to ZnCl loading by a wet impregnation method. X-ray diffraction (XRD) patterns revealed the formation of crystalline anatase phase TiO. Field emission scanning electron microscopy (FESEM) showed the formation of agglomerated spheroid shaped particles having a size in the range of 25-45 nm. Transmission electron microscopy (TEM) validates cubical faceted and nanospheroid-like morphological features with clear faceted edges for the pure TiO sample. Surface loading of ZnCl on spheroid TiO nanoparticles is evident in the case of the ZnCl loaded TiO sample. X-ray photoelectron spectroscopy (XPS) confirmed the presence of Ti and Zn species in the ZnCl loaded TiO catalyst. Energy-dispersive X-ray (EDS) spectroscopy also confirmed the existence of Ti, O, Zn and Cl elements in the nanostructured catalyst. 15% ZnCl loaded TiO afforded the highest 97% yield for 3-(1-morpholino-3-phenylprop-2-ynyl)phenol, 2-(1-morpholino-3-phenylprop-2-ynyl)phenol and 4-(1,3-diphenylprop-2-ynyl)morpholine under solvent-free and aerobic conditions. The proposed nanostructure-based heterogeneous catalytic reaction protocol is sustainable, environment-friendly and offers economic viability in terms of recyclability of the catalyst.
在无溶剂条件下，利用负载ZnCl的TiO纳米材料一锅法绿色合成炔丙胺已有效实现。芳香醛、胺和苯乙炔在所得催化剂存在下于100℃反应生成炔丙胺。纳米晶TiO最初通过溶胶-凝胶法由异丙醇钛（TTIP）合成，然后通过湿浸渍法进行ZnCl负载。X射线衍射（XRD）图谱显示形成了结晶锐钛矿相TiO。场发射扫描电子显微镜（FESEM）表明形成了尺寸在25 - 45nm范围内的团聚球形颗粒。透射电子显微镜（TEM）验证了纯TiO样品具有立方刻面和类似纳米球的形态特征，刻面边缘清晰。在负载ZnCl的TiO样品中，明显可见ZnCl在球形TiO纳米颗粒上的表面负载。X射线光电子能谱（XPS）证实了负载ZnCl的TiO催化剂中存在Ti和Zn物种。能量色散X射线（EDS）光谱也证实了纳米结构催化剂中存在Ti、O、Zn和Cl元素。在无溶剂和好氧条件下，负载15% ZnCl的TiO对3-(1-吗啉基-3-苯基丙-2-炔基)苯酚、2-(1-吗啉基-3-苯基丙-2-炔基)苯酚和4-(1,3-二苯基丙-2-炔基)吗啉的产率最高可达97%。所提出的基于纳米结构的多相催化反应方案具有可持续性、环境友好性，并且在催化剂的可回收性方面具有经济可行性。
