Synthesis, X-ray crystallographic, spectroscopic and computational studies of aminothiazole derivatives
Synthesis, X-ray crystallographic, spectroscopic and computational studies of aminothiazole derivatives
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DOI：
10.1016/j.molstruc.2016.11.046
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发表时间：
2017-03-05
影响因子：
3.8
通讯作者：
Halim, Mohammad A.
中科院分区：
文献类型：
--
作者：
Adeel, Muhammad;Braga, Ataualpa A. C.;Halim, Mohammad A.
氨基噻唑类有机化合物具有多种生物学应用。本文报道了通过铃木-宫浦交叉偶联反应合成了两个氨基噻唑衍生物：4-(联苯基-4-基)噻唑-2-胺(1)和4-(2‘，4’-difluorobipheny1-4-yl)thiazol-2-amine(2)。化合物1和2的化学结构经(H核磁共振)-H-1，(CNMR)-C-13，FT-IR，UV-Vis和单晶X-射线确证。X射线衍射研究表明，由于分子内氢键(H.B)的存在，固态结构(1)和(2)都扩散形成多链结构。此外，在M06-2X/6-311G(d，p)、B3LYP/6-31G(D)、B3LYP/6-31G(d，p)和B3LYP/6-311G(2d，p)水平上对这些化合物进行了密度泛函理论分析，得到了优化的几何、电子和光谱性质。DFT优化后的几何构型支持实验的X射线衍射谱参数。自然键轨道(NBO)计算预测了所有衍生物中的超共轭相互作用和氢键。FTIR和热力学研究也证实了二聚体中存在氢键网络，这与X射线衍射的结果一致。此外，UV-Vis分析表明，HOMO->；LUMO(98%)和HOMO->；LUMO(97%)分别在1和2处激发最大，与实验数据吻合较好。两种分子的一阶超极化率都明显大于尿素的超极化率。由前线分子轨道得到的全局反应参数揭示了这些分子可能具有生物活性。(C)2016爱思唯尔B.V.保留所有权利。
Aminothiazole organic compounds have diverse biological applications. Herein we report the synthesis of two aminothiazole derivatives: 4-(biphenyl-4-yl)thiazol-2-amine (1) and 4-(2',4'-difluorobipheny1-4-yl)thiazol-2-amine (2) via Suzuki-Miyaura cross coupling reaction. The chemical structures of 1 and 2 are confirmed using (HNMR)-H-1, (CNMR)-C-13, FT-IR, UV Vis and single crystal x-ray studies. The XRD study reveals that the both solid state structures (1) and (2) are diffused to form poly chain structures due to presence of intra molecular hydrogen bonding (H.B). Furthermore, these compounds were analysed by density functional theory (DFT) at M06-2X/6-311G(d,p), B3LYP/6-31G(d) B3LYP/6-31G(d,p) and B3LYP/6-311G(2d,p) level of theories to obtain optimized geometry, electronic and spectroscopic properties. DFT optimized geometry supports the experimental XRD parameters. Natural bond orbital (NBO) calculation predicted the hyper conjugative interaction and hydrogen bonding in all derivatives. The FTIR and thermodynamic studies also confirm the presence of hydrogen bonding network in the dimers which agrees well with the XRD results. Moreover, UV Vis analysis reveals that maximum excitations take place in 1 and 2 due to HOMO -> LUMO(98%) and HOMO -> LUMO(97%) respectively which show good agreement to experimental data. The first order hyperpolarizability of both molecules is remarkably greater than the value of urea. The global reactivity parameters which are obtained by frontier molecular orbitals disclose that the molecules might be bioactive. (C) 2016 Elsevier B.V. All rights reserved.