有机锡1,1′-亚甲基双(1h-吡唑-4-甲酸酯)的合成、结构与抗肿瘤活性

表征。配合物1和3的X射线单晶衍射分析表明，这2个配合物中的AB氮原子均没有参与配位，但它们的｛酸根却表现出明
显不同的配位方式。配合物1中｛酸根为单齿配，且该配合物表现为简单双核结构；配合物3中｛酸根为双齿配体，其通过竣
基的桥式双齿配位
成具有32元大环结构单 的二维配位高分子。初步的生物活性测试表明，这些有机锡衍生物对MCF-
756
无机化学学报
第36卷
0 Introduction
The chemistry of organotin carboxylates continues to be an active research area in recent years because of their versatile structures789 as well as significant biological activities729, especially anticancer activity7349. Recently, the synthesis of organotin carboxylates of multifunctional carboxylic acids with additional 0, S or N donor groups is drawing more and more attention due to the functionalized carboxylic acids showing variable coordination modes as well as notable bioactivities75"109. Among these functionalized carboxylic acids, pyrazolyl carboxylic acids have attracted a special interest owing to the important biological activity of pyrazole derivatives7119 as well as the good coordinating ability of pyrazole7129. Many organotin carboxylates derived from pyrazolyl carboxylic acids have been synthesized and characterized, which demonstrated fascinating structural features and excellent biological activities713"219, such as antitumor7219 and antifungal activities7149. Polycarboxylic acids have been extensively used as multifunctional ligands in designing novel and fascinating supramolecular structures with special properties7229. Many organotin polycarboxylates based on di", tri" and tetracarboxylic acids have been reported in the literatures723"289, which display interesting supramolecular architectures. It is known that the structures and biochemical behaviors of organotin carboxylates significantly depend on the type of the substituents attached to the tin atom and also on the kind of carboxylate ligands73"49. As an extension of our investigations on biologically active organotin derivatives7109, we herein report the synthesis, structure and antitumor activity in vitro of organotin 1,1"-methylenebis(1'-pyrazole-4-carboxylates).
7和A549细胞具有很好的体外细胞毒性。
关键词：氮配体；有机锡｛酸酯；晶体结构；抗肿瘤活性
中图分类号：0614.432
文献标识码：A
文章编号：1001-4861(2020)04-0755-07
DOI： 10.11862/CJIC.2020.089
Synthesis, Structure and Antitumor Activity of Organotin 1,1! -Methylenebis(1!-pyrazole-4-carboxylates)
Abstract： Four triorganotin 1,1' -methylenebis( 1 !-pyrazole-4-carboxylates) (CH2(PzCO2SnR3)2, R=Ph (1), cyclohexyl (2), Et (3), n-Bu (4)) have been synthesized via the reaction of R3SnOH or (R3Sn)2O with l,l'-methylenebis(l!pyrazole-4-carboxylic acid). All these complexes were characterized by elemental analysis, IR and multinuclear NMR (1H, 13C and 119Sn). The structures of 1 and 3 have been confirmed by the X-ray single crystal diffraction analysis, suggesting that the pyrazoyl nitrogen atoms don't participate in coordination to the tin atoms, and the carboxylate groups show considerably different coordination modes in these two complexes. In addition, complex 1 only shows a dinuclear structure, while complex 3 forms a 2D-coordination polymer with 32-membered macrocyclic units through the bridging carboxylate oxygen atoms. The cytotoxic activity of these complexes for MCF-7 and A549 cells was tested, showing that they displayed good cytotoxicities for these two cells in vitro. CCDC： 1949278, 1; 1949279, 3.
第36
4期
2020 4 月
无机 化 学 学 报 CHINESE JOURNAL OF INORGANIC CHEMISTRY

Vol.36 No.4 755-761
有机锡1,1!-亚甲基双(1!-毗)-4 "甲酸酯)
的合成、结构与抗肿瘤活性
谢运甫1唐良富**，2
(#天津科技大学理学院，天津 300457) (2南开大学化学学院，元素有机化学国家重：实验室，天津300071)
摘要：通过1,1'-亚甲基双(1H-AB-4-甲酸)(CH2(PzCO2H)2)与R&SnOH或(R&Sn)2O的反应，合成了 4个有机锡1,1'-亚甲基双(1!毗B-4-甲酸酯)衍生物(CH2(PzCO2SnR&)2,R=Ph (1),环己基⑵,Et⑶，"-Bu (4))。通过红外和核磁对这些配合物进行了详细的结构
Keywords： N ligand; organotin carboxylate; X-ray crystal structure; antitumor activity
收稿日期：2019-09-03o收修改稿日期：2019-12-23o 天津市教委资助项目(No.20140503)。 *通信联系人"E-mail:lftang@；会员登记号：S060015703M。
XIE Yun-Fu1 TANG Liang-Fu*，2
(College of Science, Tianjin University of Science and Technology, Tianjin 300457, China) (2State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China)