CN103804419B - 2-(4-溴苯基)喹啉-4-甲酸配合物及其制备方法和应用 - Google Patents
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Abstract
本发明涉及一种2-(4-溴苯基)喹啉-4-甲酸配合物及其制备方法和应用,配合物结构式如下:
Description
技术领域
本发明涉及一种2-(4-溴苯基)喹啉-4-甲酸配合物及其制备方法和应用。
背景技术
有机–金属配位化合物因其独特的理化特性,在非线性光学、分子磁体、分子开关、气体的存储与分离等材料学领域有着重要的应用价值。许多具有治疗作用的金属离子因其毒性大,刺激性强,难吸收等缺点而不能直接应用于临床,但若将其变成配合物后就能降低其毒性和刺激性。1965年,Rosenberg发现顺铂(顺式二氯二氨合铂)能有效抑制大肠杆菌的细胞分裂,随后确认了其抗癌活性,并于1971年首次在临床试验中验证了顺铂对癌细胞的抑制作用,由此药物配合物成为药物分子设计及合成的一个热门领域。(a)Rosenberg,B.;Camp,L.V.;Krigas,T.Nature1965,205,698;(b)Chen,Z.F.;Shi,Y.F.;Liu,Y.C.;Hong,X.;Geng,B.;Peng,Y.;Liang,H.Inorg.Chem.2012,51,1998;(c)Oehninger,L.;Rubbiani,R.;Ott,I.Dalton,Trans.2013,42,3269;(d)Melaiye,A.;Sun,Z.;Hindi,K.;Milsted,A.;Ely,D.;Reneker,D.H.;Tessier,C.A.;Youngs,W.J.J.Am.Chem.Soc.2005,127,2285.(e)Chen,S.C.;Zhang,Z.H.;Chen,Q.;Wang,L.Q.;Xu,J.;He,M.Y.;Du,M.;Yang,X.P.;Jones,R.A.Chem.Commum.2013,49,1270.的文件中均公开了顺铂能有效抑制大肠杆菌的细胞分裂,随后确认了其抗癌活性。
选用配合物作为新型药物开发具有如下优势:1)药物分子与金属配位形成配合物后,药物的亲脂性增大,可以提高药物分子穿透细胞膜的能力,进而提高药物的生物利用度;2)药物配合物兼具有机活性基团和无机金属离子的功效,两者间的协同效应可以克服药物分子的在临床上的耐药性和副作用。Mehrotra,R.;Shukla,S.N.;Gaur,P.;Dubey,A.Eur.J.Med.Chem.2012,50,149和Patra,M.;Gasser,G.;Metzler-Nolte,N.DaltonTrans.,2012,41,6350.公开了新型药物开发的优势。
(a)Skyrianou,K.C.;Efthimiadou,E.K.;Psycharis,V.;Terzis,A.;Kessissoglou,D.P.;Psomas,G.J.Inorg.Biochem.2009,103,1617;(b)Pidathala,C.;Amewu,R.;PacorelB.;Nixon,G.L.;Gibbons,P.;Hong,W.D.;Leung,S.C.;Berry,N.G.,J.Med.Chem.2012,55,1831;(c)Sun,J.;Zhu,H.;Yang,Z.M.;Zhu,H.L.Eur.J.Med.Chem.2013,60,23均公开了喹啉衍生物易与生物体内各种酶或受体通过疏水作用、π···π堆积及氢键作用产生抗菌、抗肿瘤、酶抑制等作用,是一种具有较强药理活性的杂环化合物。羧基与金属配位时能以单齿、螯合或桥连形式配位,全部或部分去质子化从而展现出不同的配位几何,是配位化学中最常用的配位基团。此外,羧基形成非共价键的能力也很强,易与靶点蛋白活性位点上的氨基酸形成较强的氢键相互作用。因此喹啉羧酸类衍生物具有较好的应用前景,对此进行深入研究具有一定的理论和实际价值,尤其是合成系列喹啉羧酸衍生物的配合物并对它们的生物活性进行系统的研究具有十分重要的意义。
发明内容
本发明的目的在于提供一种2-(4-溴苯基)喹啉-4-甲酸配合物及其制备方法和应用,能用于抗菌药物的制备,合成简单,便于提纯,产率较高,并且在空气中稳定性好;与配体相比,配合物的抗菌性能显著提高,金属离子在抗菌活性中起调控作用。
本发明一种2-(4-溴苯基)喹啉-4-甲酸的配合物,配合物结构式如下:
其中:M为金属。
M为Mn、Co、Cd或Zn。
2-(4-溴苯基)喹啉-4-甲酸的配合物的制备方法,步骤如下:
(1)将靛红、4-溴苯乙酮和氢氧化钾混合,加入乙醇和水加热回流10-12小时。反应结束后,反应液倒入水中,用1-2摩尔/升的盐酸调pH值4.0-5.0,沉淀过滤水洗,得到黄色固体2-(4-溴苯基)喹啉-4-甲酸。
(2)2-(4-溴苯基)喹啉-4-甲酸和金属醋酸盐溶于甲醇中,常温下搅拌3-5分钟,过滤,室温静置3-7天,得到本发明的喹啉羧酸配合物晶体。
本发明的反应方程式如下:
靛红、4‐溴苯乙酮、氢氧化钾的摩尔比为4‐4.5:1‐1.5:20‐22;
靛红的摩尔数、乙醇的体积和水的体积比为4‐4.5:1‐2:9‐12。
2‐(4‐溴苯基)喹啉‐4‐甲酸、金属醋酸盐摩尔比为1‐2:1‐2。
2‐(4‐溴苯基)喹啉‐4‐甲酸的摩尔数与甲醇的体积比为1‐1.5:150‐200。
用元素分析(C,H,N)、红外、X-射线单晶衍射表征并证实了2-(4-溴苯基)喹啉-4-甲酸配合物的结构。
本发明所述的2‐(4‐溴苯基)喹啉‐4‐甲酸的配合物用于抗菌药物。
本发明的2-(4-溴苯基)喹啉-4-甲酸合锰的配合物对革兰氏阳性菌中的枯草芽孢杆菌有较好的抑制效果,半数抑制浓度为11.29ug/mL;2-(4-溴苯基)喹啉-4-甲酸合钴的配合物具有光谱抗菌活性,对金黄葡萄球菌和大肠杆菌具有抑制效果,半数抑制浓度分别为12.27ug/mL和7.92ug/mL;2-(4-溴苯基)喹啉-4-甲酸合锌及2-(4-溴苯基)喹啉-4-甲酸合镉的配合物对革兰氏阳性菌中枯草芽孢杆菌的半数抑制浓度分别为2.32和2.65ug/mL;2-(4-溴苯基)喹啉-4-甲酸合锌及2-(4-溴苯基)喹啉-4-甲酸合镉的配合物对金黄葡萄球菌有较好的抑制效果,半数抑制浓度分别为0.57和0.51ug/mL,其中对金黄葡萄球菌的半数抑制浓度与阳性对照青霉素、链霉素相当。
与现有技术相比,本发明具有以下有益效果:
本发明的2-(4-溴苯基)喹啉-4-甲酸配合物合成简单,便于提纯,产率较高,并且在空气中稳定性好;与配体相比,配合物的抗菌性能显著提高,甚至和阳性对照药物相当。金属离子在抗菌活性中起调控作用。我们可以通过配体的修饰,进一步研究此类配合物的构效关系,不断改进配合物的抑菌性能,在新型抗菌药物筛选中具有较好的应用前景。
附图说明
图1为实施例1的单晶结构图;
图2为实施例2的单晶结构图;
图3为实施例3的单晶结构图;
图4为实施例4的单晶结构图。
具体实施方式
下面结合实施例对本发明做进一步说明,但本发明的范围并不受这些实施例的任何限制。
检测所用仪器为:Perkin-Elmer240C型元素分析仪,Vector22Bruker分光光度计(400-4000cm-1),以及BrukerSmartApexCCD单晶衍射仪等。
实施例1:
2-(4-溴苯基)喹啉-4-甲酸合锰(Ⅱ)
(1)将靛红(1.18g,8.00mmol),4-溴苯乙酮(0.40g,2.00mmol),氢氧化钾(2.24g,40.00mmol)溶于2mL乙醇和18mL水的混合溶液中,加热回流反应12小时,冷却后,反应液倒入20mL水中,以1M的盐酸调节体系pH到4,产生的沉淀过滤,水洗得黄色固体2-(4-溴苯基)喹啉-4-甲酸597mg,产率:91%;
检测2-(4-溴苯基)喹啉-4-甲酸得IR(KBr,cm-1):3445,2361,1714,1588,1544,1490,1403,1367,1227,1197,1075,1007,831,802,766,713,541,514.1HNMR(500MHz,DMSO,δ):8.65(d,J=8.0Hz,1H),8.46(s,1H),8.27(d,J=8.5Hz,2H),8.17(d,J=8.0Hz,1H),7.87(t,1H),7.77(d,J=8.5Hz,2H),7.21(t,1H).Anal.CalcdforC16H10BrNO2:C,58.56;H,3.07;N,4.27.Found:C,58.67;H,3.04;N,4.29%;
(2)将2-(4-溴苯基)喹啉-4-甲酸(13.1mg,0.04mmol)溶于7mL甲醇中,加入到醋酸锰(9.8mg,0.04mmol)的4mL甲醇溶液中,室温搅拌3分钟,过滤,静置3天,出现10.0-11.0mg黄色晶体,过滤,并用甲醇洗涤三次,置于无水氯化钙干燥器内干燥得产品。产率66%。
产品经过元素分析结果:计算值:C(%),52.81;H(%),3.39;N(%),3.62;
实测值:C(%),52.96;H(%),3.37;N(%),3.63
IR(KBr,cm-1):3440,3061,2361,1639,1587,1403,1322,1072,1029,1005,809,760,662,466。
实施例2:
2-(4-溴苯基)喹啉-4-甲酸合钴(Ⅱ)
步骤(1)与实施例1的步骤(1)相同;
步骤(2)将2-(4-溴苯基)喹啉-4-甲酸(13.1mg,0.04mmol)溶于6mL甲醇中,加入到醋酸钴(10.0mg,0.04mmol)的4mL甲醇溶液中,室温搅拌4分钟,过滤,静置4天,出现6.0-8.0mg黄色晶体,过滤,并用甲醇洗涤三次,置于无水氯化钙干燥器内干燥得产品。产率45%。
产品经过元素分析结果:计算值:C(%),52.53;H(%),3.37;N(%),3.60;
实测值:C(%),52.69;H(%),3.35;N(%),3.62
IR(KBr,cm-1):3446,3065,2361,1645,1603,1536,1464,1404,1367,1032,810,759,666,468。
实施例3:
2-(4-溴苯基)喹啉-4-甲酸合锌(Ⅱ)
步骤(1)与实施例1的步骤(1)相同;
步骤(2)将2-(4-溴苯基)喹啉-4-甲酸(13.1mg,0.04mmol)溶于8mL甲醇中,加入到醋酸锌(8.8mg,0.04mmol)的4mL甲醇溶液中,室温搅拌3分钟,过滤,静置3天,出现11.0-12.0mg黄色晶体,过滤,并用甲醇洗涤三次,置于无水氯化钙干燥器内干燥得产品。产率72%。
产品经过元素分析结果:计算值:C(%),52.10;H(%),3.34;N(%),3.57;
实测值:C(%),52.31;H(%),3.32;N(%),3.58;
IR(KBr,cm-1):3445,3063,2361,1651,1588,1547,1403,1321,1106,1073,1029,810,761,665,469。
实施例4:
2-(4-溴苯基)喹啉-4-甲酸合镉(Ⅱ)
步骤(1)与实施例1的步骤(1)相同;
步骤(2)将2-(4-溴苯基)喹啉-4-甲酸(13.1mg,0.04mmol)溶于6mL甲醇中,加入到醋酸镉(10.7mg,0.04mmol)的4mL甲醇溶液中,室温搅拌3分钟,过滤,静置3天,出现10.0-12.0黄色晶体,过滤,并用甲醇洗涤三次,置于无水氯化钙干燥器内干燥得产品。产率68%。
产品经过元素分析结果:计算值:C(%),49.15;H(%),3.15;N(%),3.37;
实测值:C(%),49.34;H(%),3.13;N(%),3.39;
IR(KBr,cm-1):3445,2361,1586,1542,1486,1400,1316,1103,1072,1010,900,808,759,663,469。
表1为实施例1-4所述的四种2-(4-溴苯基)喹啉-4-甲酸的金属配合物。
表1实施例1-4的2-(4-溴苯基)喹啉-4-甲酸金属配合物
序号 | 金属盐 | 配合物 | 性状 | 产率(%) |
实施例1 | Mn(CH3COO)2·2H2O | (C68H52O12N4Br4)Cd2 | 淡黄色晶体 | 68 |
实施例2 | Co(CH3COO)2·H2O | (C68H52O12N4Br4)Zn2 | 深红色晶体 | 65 |
实施例3 | Zn(CH3COO)2·4H2O | (C68H52O12N4Br4)Co2 | 淡黄色晶体 | 58 |
实施例4 | Cd(CH3COO)2·2H2O | (C68H52O12N4Br4)Mn2 | 淡黄色晶体 | 64 |
下面对实施例1-4进行检测。
1、2-(4-溴苯基)喹啉-4-甲酸配合物的单晶结构表征
测试仪器为BrukerSmartApexCCD单晶衍射仪,以Mo-Kα(λ=0.071073nm)射线,在20℃时用ω/2θ的扫描模式进行测试。数据通过SAINT修正,Lorentz修正和极化效应的消除得到。吸收修正使用Bruker的SADABS补充。用SHELXL-97直接解出了分子结构。金属原子及其周围相连原子的位置用直接E-maps的方法测出,其他非氢原子通过傅立叶变换,最小二乘法修正逐步确定其精细结构。氢原子则最后确定于计算所得的位置,并有统一的Uiso值,溶剂的氢原子由差值傅里叶图中确定。检测结果如表2所示。
表2实施例1-4的单晶衍射数据表
aR1=Σ||C|-|Fc||/ΣFo|.bwR2=[Σw(Fo 2-Fc 2)2/Σw(Fo 2)]1/2。
2、本发明2-(4-溴苯基)喹啉-4-甲酸配合物对枯草芽胞杆菌(B.subtilis),金黄葡萄球菌(S.aureus),铜绿假单胞菌(P.aeruginosa)和大肠杆菌(E.coli)的作用检测;
测试方法及步骤:取培养的枯草芽胞杆菌(B.subtilis),金黄葡萄球菌(S.aureus),铜绿假单胞菌(P.Aeruginosa)和大肠杆菌(E.coli)的菌株,分别稀释成2×104个/mL,分装于96孔板,孔板为0.1mL/孔,每孔10μL。各组设3个平行孔,置37℃恒温培养箱中培养24h,加入5mg/mL的MTT液40μL/孔,再培养4h。取出培养板,离心,倒掉上层清液,加入DMSO150μL/孔,在570nm波长下,用美国生产的BioRad550型酶标仪测出OD值,计算得到不同喹啉金属配合物的半数抑制浓度,其中青霉素和链霉素作为阳性对照组。
半数抑制浓度越小,化合物的抗菌性越好。原料、实施例1-4所得产品、对照组抑菌活性测试结果如表3。
表3原料、实施例1-4和对照组的抑菌活性测试结果
Claims (7)
1.一种2-(4-溴苯基)喹啉-4-甲酸配合物,其特征在于,配合物结构式如下:
其中,M为Mn、Co、Cd或Zn。
2.一种权利要求1所述的2-(4-溴苯基)喹啉-4-甲酸配合物的制备方法,其特征在于,步骤如下:
(1)将靛红、4-溴苯乙酮和氢氧化钾混合,加入乙醇和水加热回流10-12小时,反应结束后,反应液倒入水中,用1-2摩尔/升的盐酸调pH值4.0-5.0,沉淀过滤水洗,得到黄色固体2-(4-溴苯基)喹啉-4-甲酸;
(2)2-(4-溴苯基)喹啉-4-甲酸和金属醋酸盐溶于甲醇中,常温下搅拌3-5分钟,过滤,室温静置3-7天,得到本发明的喹啉羧酸配合物晶体。
3.根据权利要求2所述的2-(4-溴苯基)喹啉-4-甲酸配合物的制备方法,其特征在于,靛红、4-溴苯乙酮、氢氧化钾的摩尔比为4-4.5:1-1.5:20-22。
4.根据权利要求2所述的2-(4-溴苯基)喹啉-4-甲酸配合物的制备方法,其特征在于,靛红的摩尔数、乙醇的体积和水的体积比为4-4.5:1-2ml:9-12ml。
5.根据权利要求2所述的2-(4-溴苯基)喹啉-4-甲酸配合物的制备方法,其特征在于,2-(4-溴苯基)喹啉-4-甲酸、金属醋酸盐摩尔比为1-2:1-2。
6.根据权利要求2所述的2-(4-溴苯基)喹啉-4-甲酸配合物的制备方法,其特征在于,2-(4-溴苯基)喹啉-4-甲酸的摩尔数与甲醇的体积比为1-1.5:150-200ml。
7.一种权利要求1所述的2-(4-溴苯基)喹啉-4-甲酸配合物的应用,其特征在于,2-(4-溴苯基)喹啉-4-甲酸配合物用于制备抗菌药物。
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US4221785A (en) * | 1978-05-30 | 1980-09-09 | Sorenson John R J | Anti-inflammatory and anti-ulcer compounds and process |
CN102643297A (zh) * | 2012-03-07 | 2012-08-22 | 上海师范大学 | 一种具有荧光的抗菌铜三元配合物及其制备方法和应用 |
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2014
- 2014-03-13 CN CN201410092408.6A patent/CN103804419B/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4221785A (en) * | 1978-05-30 | 1980-09-09 | Sorenson John R J | Anti-inflammatory and anti-ulcer compounds and process |
CN102643297A (zh) * | 2012-03-07 | 2012-08-22 | 上海师范大学 | 一种具有荧光的抗菌铜三元配合物及其制备方法和应用 |
Non-Patent Citations (2)
Title |
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Crystal structure, spectroscopic, and biological study of the copper(II) complex with third-generation quinolone antibiotic sparfloxacin;Eleni K. Efthimiadou et al.;《Bioorganic & Medicinal Chemistry Letters》;20060511;第16卷;第3864-3867页 * |
Tetrakis(μ-2-phenylquinoline-4-carboxylato-κ2O:O)bis[(methanol-O)copper(II)];Junfang Guo et al.;《Acta Crystallographica Section E》;20120926;第m1296页 * |
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