具有复合性能的新型三脚架型多苯并咪唑季铵盐类化合物的合成、表征和应用

doi:10.11944/j.issn.1000-0518.2015.08.140402

摘要/Abstract

摘要：

合成了15种新型三脚架结构苯并咪唑季铵盐类化合物(3a~3o)。通过IR、NMR和HRMS等技术手段对目标产物(3a~3o)进行了结构表征。并对目标化合物调节植物生长活性进行了评价。结果表明, 目标化合物浓度为10 mg/L时, 化合物3a、3c、3f、3g、3h、3i和3j均具有优良的促细胞分裂活性, 最高达88.3%, 比参照物三唑酮(50.2%)的促细胞分裂活性更高, 但生长素活性不明显;目标化合物均具有优异的除草活性, 其中化合物3i效果最明显, 可以达到95.6%。同时利用荧光光谱, 探究了4种代表性目标分子对人体中常见的6种阴离子的荧光识别, 结果发现目标化合物能较好的识别I^-, 可作为I^-荧光识别探针。

关键词: 苯并咪唑, 生物活性, 植物生长调节, 阴离子识别

Abstract:

Fifteen new tripod type benzimidazolium salts(3a~3o) were synthesized and characterized by IR, NMR and HRMS. The plant growth regulating activities of compound 3 were evaluated. Compounds 3a, 3c, 3f, 3g, 3h, 3i and 3j exhibit excellent cytokinesis activities up to 88.3% at the concentration of 10 mg/L which are higher than that of the reference triadimefon(50.2%), but their auxin activities are not obviously effective. Nearly all the target compounds have excellent herbicidal activity, while compound 3i is the best with 95.6%. The fluorescent identification of the four representative target molecules on six important anions was explored by fluorescence spectrum. The target compounds can be used as fluorescence probe for I^- identification.

Key words: benzimidazole, biological activity, plant growth regulator, anionic identification

中图分类号:

张成路, 孙丽杰, 松布尔, 国阳, 赵宝成, 唐杰, 袭焕. 具有复合性能的新型三脚架型多苯并咪唑季铵盐类化合物的合成、表征和应用[J]. 应用化学, 2015, 32(8): 873-883.

ZHANG Chenglu, SUN Lijie, SONG Buer, GUO Yang, ZHAO Baocheng, TANG Jie, XI Huan. Synthesis and Application of Novel Tripod-type Benzimidazolium Compounds[J]. Chinese Journal of Applied Chemistry, 2015, 32(8): 873-883.

参考文献

[1]	Buchanan B B, Gruissem W, Jones R L. Biochemistry & Molecular Biology of Plants[M]. USA:American Society of Plant Biologists, 2000.
[2]	Davies P J. Plant hormones:Physiology, Biochemistry and Molecular Biology and Edition[M].USA:Kluwer Academic Publishers, 1995.
[3]	CHENG Zhiming, GU Baoquan, LI Haizhou. The Synthesis of Acetamiprid[J]. Pesticides, 1998, 37(9):12-14(in Chinese). 程志明, 顾保权, 李海舟. 吡虫清的合成[J]. 农药, 1998, 37(9):12-14.
[4]	Sandoz A G. Nouveaux Agents Regulateurs de la Croissance des Plantes a Base de Derives du Triazole:BR 8101239[P], 1981.
[5]	NI Qingling, TAO Jie, SHI Min, et al.Synthesis and Antibacterial Activity of 1-(Pyridine-3-methyl)-2-ethylbenzimidazole[J]. J Guangxi Normal Univ, 2009, 27(2):72-75(in Chinese). 倪青玲, 陶杰, 石敏, 等. 1-(吡啶-3-甲基)-2-乙基苯并咪唑的合成及抑菌活性[J]. 广西师范大学学报, 2009, 27(2):72-75.
[6]	ZHANG Chenglu, ZHU Chang'an, WU Feiyu, et al. Synthesis, Biological Activity and Electrochemical Properties of Ferrocenyl 1, 3, 4-Triazoles Derivatives[J]. Chinese J Appl Chem, 2014, 31(4):455-461(in Chinese). 张成路, 朱长安, 武飞宇, 等. 二茂铁基1, 3, 4-三唑席夫碱衍生物合成及生物活性和电化学性质[J]. 应用化学, 2014, 31(4):455-461.
[7]	Thies R W, Collins G R, Sekin T, et al.Synthesis of 2, 2-Bis[4-(3, 4-diaminophenoxy) phenyl]propane and Its Polymerization[J]. Macromolecules, 1992, 25(4):1207-1213.
[8]	Tebbe M J, Jensen C B, Spitzer W A, et al.The Effects of Antirhino- and Enteroviral Vinylacetylene Benzimidazoles on Cytochrome P450 Function and Hepatic Porphyrin Levels in Mice[J]. Antiviral Res, 1999, 42(1):25-33.
[9]	ZHU Li, LIAO Zhanru, LONG Yunfei, et al.Syntheses and Crystal Stuctures of Znic(Ⅱ) Complex Containing Benzimidazolyl[J]. Chinese J Inorg Chem, 2004, 20(4):399-402(in Chinese). 朱莉, 廖展如, 龙云飞, 等. 含苯并咪唑锌配合物的合成、表征及晶体结构[J]. 无机化学学报, 2004, 20(4):399-402.
[10]	Spasov A A, Yozhitsa I N, Bugaeva L I, et al.Search for New Durgs Benzimidazole Derivatives: Spectrum of Pharmarcological Activity and Toxicological Properties(A Review)[J]. Pharm Chem, 1999, 33(5):232-243.
[11]	Assmann L, Marhold A, Dehne H W. Substituted Benzimidazoles for Pest Control:US, 6103745[P], 2000.
[12]	WANG Luyao, LI Xiaojuan, CHEN Bang, et al.Synthesis, Crystal Structure and Antimicrobial Activity of Two Novel 2-Naphthalenemethyl Benzimidazole Derivatives[J]. Chinese J Appl Chem, 2005, 22(10):586-589(in Chinese). 王陆瑶, 李小娟, 陈邦, 等. 苯并咪唑衍生物的合成、表征及其杀菌活性[J]. 应用化学, 2005, 22(10):586-589.
[13]	Mobinikhaledi A, Foroughifar N, Kalhor M. Synthesis and Antifungal Activity of Novel 2-Benzimidazolylimino-5-arylidene-4-thiazolidinones[J]. J Hetercycl Chem, 2010, 47(1):77-80.
[14]	CHEN Lan, WEI Ningning, GAO Jie, et al.Synthesis and Antifungal Activity of 2-Heterocyclicbenzimidazole Derivatives[J]. Chinese J Pest Sci, 2011, 13(5):448-452(in Chinese). 陈岚, 魏宁宁, 高洁, 等. 2-取代苯并咪唑类化合物的合成及其抑菌活性[J]. 农药学学报, 2011, 13(5):448-452.
[15]	GAO Juanli. Synthesis and Antibacterial Activities of Bis-benzimidazole Derivatives[D]. Northwest Agricuture and Forest Science and Technology University, 2012(in Chinese). 高娟丽. 双苯并咪唑类衍生物的合成及其抑菌活性研究[D]. 西北农林科技大学, 2012.
[16]	YAN Xuankai. Synthesis and Antifungal Activities of (1H-Benzo[d]imidazol-2-yl) Alkyl Amine Derivatives[D]. Northwest Agricuture and Forest Science and Technology University, 2012(in Chinese). 阎宣凯. (1H-苯并咪唑-2-基)烷胺衍生物的合成及抑菌活性研究[D]. 西北农林科技大学, 2012.
[17]	Pearson C J, Cramp M C, Luheshi A. Preparation of 2-(1-Sufamoyl benzimidazol 2-2 yl)pyridine-3-carboxylates and Related Compounds as Herbicides:EP, 508800[P].1992.
[18]	YAN Yixin, HAN Xiuying, ZHAO Xiugai, et al.Synthesis and Application of Quaternary Ammonium Plant Growth Regulator[J]. Fine Chem, 2001, 18(6):311-313(in Chinese). 阎一新, 韩秀英, 赵秀改, 等. 季铵盐型植物生长调节剂的合成及应用研究[J]. 精细化工, 2001, 18(6):311-313.
[19]	YE Xiangyang, GUO Qizhen. Quaternary Ammonium Plant Growth Regulator[J]. Pest Sci, 1993, 15(2):31-36(in Chinese). 叶向阳, 郭奇珍 .季铵盐类植物生长调节剂[J]. 农药译丛, 1993, 15(2):31-36.
[20]	LIANG Zhicheng, DENG Libo, ZENG Zhaoqiong, et al.Quaternary Ammonium Synthesis and Biological Effects of Plants Growth Inhibitor Trials[J]. J South China Normal Univ(Nat Sci Edn), 1981, 1:27-31(in Chinese). 梁致诚, 邓礼波, 曾昭琼, 等. 季铵盐类植物生长抑制剂的合成及生物效应试验[J]. 华南师院学报(自然科学版)1981, 1:27-31.
[21]	YAN Yixin, DU Huizhi, BO Gaimei, et al.Study on Synthesis of an Novel Growth Regulator for Plant and Its Application[J]. J Shanxi Univ(Nat Sci Edn), 2000, 23(2):186-188(in Chinese). 阎一新, 杜会枝, 薄改梅, 等. 一种新型植物生长调节剂的合成及应用研究[J]. 山西大学学报(自然科学版), 2000, 23(2):186-188.
[22]	Hirano K, Kubota T, Tsuda M, et al.Pyrinodemins B-D, Potent Cytotoxic Bis-Pyridine Alkaloids from Marine Sponge Amphimedon sp[J]. Chem Pharm Bull, 2000, 48(7):974-977.
[23]	Fujimoto Y. Insecticide for Agriculture and Horticulture Containing Sesquiterpene Pyridine Alkaloid Compound:JP, 2000256111[P], 2000.
[24]	Martínez-Máñez R, Sancenón F. Fluorogenic and Chromogenic Chemosensors and Reagents for Anions[J]. Chem Rev, 2003, 103(11):4419-4476.
[25]	ErionM D, Dang Q, Reddy M R, et al. Structure-Guided Design of AMP Mimics That Inhibit Fructose-1, 6-bisphosphatase with High Affinity and Specificity[J]. J Am Chem Soc, 2007, 129(50):15480-15490.
[26]	Dang Q, Kasibhatla S R, Xiao W, et al.Design, Synthesis, and Structure-Activity Relationship of a Series of Phosphonic Acid Containing Benzimidazoles That Function as 5'-Adenosinemonophosphate(AMP) Mimics[J]. J Med Chem, 2010, 53(1):441-451.
[27]	Das G, Kar C, Basu A. Benzimidazole Functionalized Tripodal Receptor for Selective Recognition of Iodide[J]. Tetrahedron Lett, 2012, 53:4754-4757.