三环己基锡8-羟基喹啉配合物的微波辅助合成、结构表征、热稳定性和体外抗癌活性

doi:10.3724/SP.J.1095.2014.30495

摘要/Abstract

摘要： 微波辐射下，8-羟基喹啉与三环己基氢氧化锡反应，合成了三环己基锡配合物Cy3SnOC9NH6(Cy为环己基)。通过UV、IR、1H和13C NMR、元素分析及X射线单晶衍射等技术手段表征结构。实验结果表明，该配合物属三斜晶系，空间群P1，晶体学参数:a=0.99530(5) nm，b=1.01129(5) nm，c=2.58327(13) nm，α=89.1880(10)°，β=86.6290(10)°，γ=81.2490(10)°，Z=4，V=2.5654(2) nm3，Dc=1.326 Mg/m3，μ(MoKα)=1.013 mm-1，F(000)=1064，R1=0.0447，wR2=0.0891。配合物在200 ℃以下稳定，对人体的癌细胞Colo205、HepG2、MCF-7和NCI-H460增殖均有较强的抑制作用。

关键词: 三环己基锡8-羟基喹啉配合物, 微波辅助合成, 晶体结构, 抗癌活性

Abstract: A novel tricyclohexyltin complex Cy3SnOC9NH6 was synthesized by the reaction of 8-quinolinol with tricyclohexyltin hydroxide under microwave irradiation, and characterized by UV, IR, 1H and 13C NMR, elemental analysis and X-ray crystal diffraction. The crystal belongs to triclinic system, space group P1 with the cell parameters:a=0.99530(5) nm, b=1.01129(5) nm, c=2.58327(13) nm, α=89.1880(10)°, β=86.6290(10)°, γ=81.2490(10)°, Z=4, V=2.5654(2) nm3, Dc=1.326 Mg/m3, μ(MoKα)=1.013 mm-1, F(000)=1064, R1=0.0447, wR2=0.0891. The complex is stable up to ~200 ℃. It displays strong in vitro anticancer activity against four human cancer cell lines, Colo205, HepG2, MCF-7 and NCI-H460.

Key words: tricyclohexyltin 8-quinolinol complex, microwave assisted synthesis, crystal structure, anticancer activity

中图分类号:

O627.4

庾江喜, 冯泳兰, 邝代治, 张复兴, 蒋伍玖, 朱小明. 三环己基锡8-羟基喹啉配合物的微波辅助合成、结构表征、热稳定性和体外抗癌活性[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30495.

YU Jiangxi, FENG Yonglan, KUANG Daizhi*, ZHANG Fuxing, JIANG Wujiu, ZHU Xiaoming. Microwave Assisted Synthesis, Structural Characterization, Thermal Stability and in vitro Anticancer Activity of Tricyclohexyltin 8-Quinolinoxide[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30495.

参考文献

[1] Chandrasekhar V,Mohapatra C,Butcher R J. Synthesis of One- and Two-Dimensional Coordination Polymers Containing Organotin Macrocycles. Reactions of (n-Bu3Sn)2O with Pyridine Dicarboxylic Acids. Structure-Directing Role of the Ancillary 4,4′-Bipyridine Ligand[J]. Cryst Growth Des,2012,12(6):3285-3295.

[2] Song S Y,Ma J F,Yang J,et al. Synthesis of an Organotin Oligomer Containing a Heptanuclear Tin Phosphonate Cluster by Debenzylation Reactions:X-ray Crystal Structure of {Na6(CH3OH)2(H2O)}-{[(BzSn)3(PhPO3)5(μ3-O)(CH3O)]2Bz2Sn}·CH3OH[J]. Organometallics,2007,26(8):2125-2128.

[3] Hong M,Yin H,Zhang X,et al. Di- and Tri-organotin(Ⅳ) Complexes with 2-Hydroxy-1-Naphthaldehyde 5-Chloro-2-Hydroxybenzoylhydrazone:Synthesis, Characterization and in vitro Antitumor Activities[J]. J Organomet Chem,2013,724:23-31.

[4] PENG Bin,SUN Lijuan,CHANG Weixing,et al. Syntheses and Study of Diorganotin Ferrocenoates[J]. Chinese J Org Chem,2003,23(4):344-349(in Chinese).

彭斌,孙丽娟,常卫星,等. 二烃基锡二茂铁羧酸酯的合成及研究[J]. 有机化学,2003,23(4):344-349.

[5] LUO Ning,SUN Lijuan,LIU Zhizhong,et al. Synthesis, Characterization and Biological Activities of Trialkyltin(Ⅳ) Ferrocene Carboxylates[J]. Chinese J Appl Chem,2000,17(2):154-158(in Chinese).

罗宁,孙丽娟,刘治中,等. 三烃基锡二茂铁甲酸酯的合成、表征及其生物活性[J]. 应用化学,2000,17(2):154-158.

[6] ADAMA Moussasakho,DU Dafeng,ZHU Dongsheng,et al. The One-Dimensional Chain:Synthesis, Crystal Structure and Biological Activities of Tricyclohexyl Tin Carboxylates[J]. Chinese J Inorg Chem,2011,27(1):107-113(in Chinese).

阿达玛,杜大峰,朱东升,等. 一维链状三环己基锡羧酸酯的合成、结构及生物活性[J]. 无机化学学报,2011,27(1):107-113.

[7] GONG Genfei,SONG Ran,ZOU Yinbo,et al. Syntheses and Characterization of Cyclohexyl(phenyl)[(trimethylsilyl)methyl]stannyl Aromatic Carboxylates[J]. Chinese J Org Chem,2013,33(4):803-807(in Chinese).

龚根飞,宋冉,邹引波,等. 芳香酸环己基(苯基)[(三甲基硅基)甲基]锡酯的合成及结构[J]. 有机化学,2013,33(4):803-807.

[8] YIN Handong,MA Chunlin,ZHANG Rufen. Synthesis and Characterization of Di-(or Tri)Butyltin Alkenyl (or Alkynyl) Phosphates[J]. Chinese J Org Chem,2000,20(1):108-111(in Chinese).

尹汉东,马春林,张如芬. 二(三)丁基锡烯基(炔基)膦酸脂的合成与表征[J]. 有机化学,2000,20(1):108-111.

[9] LU Wenguan,TAO Jiaxun. Di-n-butytin 2-Ferrocenyibenzoatos: Synthesis, Characterization and in vitro Antitumour Activity[J]. Chem Res Appl,2001,13(4):372-375(in Chinese).

卢文贯,陶家洵. 二正丁基锡邻二茂铁基苯甲酸酯配合物的合成、表征及其体外抗癌活性[J]. 化学研究与应用,2001,13(4):372-375.

[10] Sun M L,Ruan B F,Zhang Q,et al. Synthesis, Crystal Structures, Electrochemical Studies and Anti-tumor Activities of Three Polynuclear Organotin(IV) Carboxylates Containing Ferrocenyl Moiety[J]. J Organomet Chem,2011,696(20):3180-3185.

[11] Hanif M,Hussain M,Ali S,et al. In vitro Biological Studies and Structural Elucidation of Organotin(Ⅳ) Derivatives of 6-Nitropiperonylic Acid:Crystal Structure of {[(CH2O2C6H2(o-NO2)COO)SnBu2]2O}2[J]. Polyhedron,2010,29(1):613-619.

[12] Zhang X Y,Song H B,Li Q S,et al. Synthesis, Structure and Biological Activity of Organotin Derivatives with Pyridylmethylthiobenzoic Acid[J]. Polyhedron,2007,26(14):3743-3749.

[13] Affan M A,Foo S W,Jusoh I,et al. Synthesis, Characterization and Biological Studies of Organotin(Ⅳ) Complexes with Hydrazone Ligand[J]. Inorg Chim Acta,2009,362(14):5031-5037.

[14] Szorcsik A,Nagy L,Scopelliti M,et al. Preparation and Structural Characterization of Organotin(Ⅳ) Complexes with Ligands Containing a Hetero {N} Atom and a Hydroxy Group or Hydroxy and Carboxyl Groups[J]. J Organomet Chem,2005,690(9):2243-2253.

[15] Baul T S B,Mizar A,Rivarola E,et al. Re-visiting of 5-[(E)-2-(aryl)-1-diazenyl]-quinolin-8-ol with Tweaking of Sn-Ph Groups:Synthesis, Spectroscopic Characterization and X-ray Crystallography[J]. J Organomet Chem,2008,693(10):1751-1758.

[16] Wang Q. Benzylchloridobis(quinolin-8-olato)tin(Ⅳ)[J]. Acta Cryst,2009,E65:m905.

[17] Kell E,Vrábel V,Holecek J,et al. The Crystal Structure of Butylchlorobis(8-quinolinate)tin(Ⅳ)[J]. J Organomet Chem,1995,493(1-2):13-16.

[18] Lycka A,Jirman J,Holecek J,et al. 119Sn,15N,13C and 1H NMR Study of Some Tri- and Di-organotin(Ⅳ) 8-Quinolinethiolates[J]. J Organomet Chem,1989,372(3):327-338.

[19] Singh R V,Chaudhary P,Poonia K,et al. Microwave-assisted Synthesis, Characterization and Biological Screening of Nitrogen-sulphur and Nitrogen-oxygen Donor Ligands and Their Organotin(Ⅳ) Complexes[J]. Spectrochim Acta A,2008,70(3):587-594.

[20] Murugavel R,Gogoi N. Microwave Assisted Solid-state Synthesis of Functional Organotin Carboxylates from Sterically Encumbered 3,5-Di-tert-butylsalicylic Acid[J]. J Organomet Chem,2008,693(19):3111-3116.

[21] LUO Huiping,WANG Yixing,LIN Zechen,et al. Four Spectra Fundamentals of Organic Chemistry[M]. Hangzhou:Zhejiang University Press,1988:7(in Chinese).

罗惠萍,王逸兴,林泽琛,等. 有机化学四谱基础[M]. 杭州:浙江大学出版社,1988:7.

[22] KE Yikan,DONG Huiru. Analysis Chemistry Handbook[M]. Vol.3. Beijing:Chemical Industry Press,1998:932-935(in Chinese).

柯以侃,董慧茹. 分析化学手册[M]. 第三分册. 北京:化学工业出版社,1998:932-935.