CN113912534B - 一种联苯类杂环化合物、其合成方法及其应用 - Google Patents

一种联苯类杂环化合物、其合成方法及其应用 Download PDF

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CN113912534B
CN113912534B CN202111325502.8A CN202111325502A CN113912534B CN 113912534 B CN113912534 B CN 113912534B CN 202111325502 A CN202111325502 A CN 202111325502A CN 113912534 B CN113912534 B CN 113912534B
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biphenyl
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heterocyclic compound
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CN113912534A (zh
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郑绍军
姜乔榉
武文斌
谈祎
杨程
韩珂
朱瑞
陈立庄
李照磊
宋恒
蒋春辉
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Jiangsu University of Science and Technology
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Abstract

本发明涉及联苯类杂环化合物、其合成方法及其应用。所述的联苯类杂环化合物的通式是

Description

一种联苯类杂环化合物、其合成方法及其应用
技术领域
本发明属于海洋污损防治技术领域，具体涉及一种联苯类杂环化合物的合成及防污技术。
背景技术
海洋生物污损是指海水中有害的微型或大型生物在物体表面的不良沉积，是人类开始从事海洋活动就遇到的生物危害，海洋生物污损的危害主要表现在以下几个方面：(1)增大了船舶的航行阻力，造成动力消耗增加。据统计，每年因为生物污损引起的额外消耗就达600亿美元，而每年用于清除和防止海洋生物污损的消耗达57亿美元。(2)由于生物污损所增加的燃料燃烧预计到2020年将增加38％～72％的CO2和SO2排放量，加剧地球变暖。(3)加剧海洋工程材料的腐蚀破坏，降低海洋设施性能。(4)将新的物种带到异地，威胁当地的生态***。目前最行之有效的防污方法就是涂刷含有机锡等有毒防污剂的防污涂料，然而这种防污涂料在防污的同时严重危害海洋生态环境。国际海事组织(IMO)明确规定，自2008年1月1日起，全球禁止使用含有机锡防污涂料。因此替代有机锡的无毒防污剂的研究开发成为当今海洋科学技术中亟待解决的重大技术问题之一。
在对付这些海洋生物污损的方法中，最普通的是使用一种内含杀生剂的涂料，借助杀生剂的释放及其对海洋生物的毒性，驱赶并杀死附着的海洋生物。联苯类杂环化合物的具有多种生物活性，可广泛的用于医药、生物农药、饮食保健、化工以及军事等领域，还可用作防污涂料。其作为防污剂的防污涂料不仅能有效地抑制和驱避海洋生物、藤壶对船底的附着污损，并且对其他污损生物也有一定抑制作用。发明人所拥有的申请号为2018104212515发明专利，公开了一种2-(3,4)-二氯苯基-4-氟苯胺的制备方法，利用铜试剂替代毒性较大的Pd试剂，完成联苯的合成；工艺简便，环保无污染。本发明是对该制备方法的进一步改进。
发明内容
针对现有问题的不足，本发明的目的是提供一种联苯类杂环化合物、其合成方法及其防污应用，采用廉价且低毒的氯化镁试剂作为催化剂，替代了毒性较大，价格昂贵的金属钯，铂等贵金属；合成工艺简便，合成成本低，环保无污染。
为了实现上述发明目的，本发明采用的技术方案是：
具有通式(I)的联苯类杂环化合物：
上述联苯类杂环化合物的合成路线如下：
所述的R为以下基团之任意一种：
具体来说，一种联苯类杂环化合物的合成方法，步骤如下：
(1)2-溴-4-氟苯胺与酸酐在室温下反应2～3h，发生酰化反应，生成所需要的酰胺化合物，目的是保护胺基，以免发生副反应。
(2)胺基保护后的2-溴-4-氟乙酰苯胺，在氯化镁试剂以及溴化亚铁和氧化剂BQ的共同作用下，发生联苯反应，生成了联苯化合物，这是本发明的关键反应。
该步骤所采用的有机溶剂选自***，四氢呋喃、二氧六烷、N,N-二甲基酰胺、丙酮、间二甲苯、二氯甲烷、二甲基乙酰胺中的任意一种。
该步骤所采用的催化剂氯化镁试剂，廉价、低毒，符合环保要求。
加入氧化剂BQ的反应温度为r.t～50℃，反应时间20～90min。
氯化镁试剂与氧化剂BQ的摩尔比为0.1～0.5:0.2～1.5。
(3)然后2-(3,4-二氯苯基)-4-氟乙酰苯胺发生水解反应，得到关键中间体，为联苯类化合物的合成提供了关键合成骨架。
(5)关键骨架2-(3,4-二氯苯基)-4-氟苯胺与不同的酸反应，生成20个目标化合物。
所述的酸为杂环的酸，对甲氧基苯甲酸，1-萘酸，3-氯异烟酸，5,6-二氯烟酸，异烟酸，5-甲基吡嗪-2-羧酸，2-羧酸吡嗪，5-氯吡嗪-2-羧酸，2-氯吡啶-6-羧酸，2-氨基烟酸，2-氟烟酸，2-氯烟酸，2-氯异烟酸，吡啶-2-羧酸，6-氯烟酸，6-甲基烟酸，5-甲基烟酸，烟酸，2-羟基烟酸，邻醛基苯甲酸。
具有通式(I)的联苯类杂环化合物具有良好的杀菌活性，所述的菌类是金黄色葡萄球菌和大肠杆菌。
有益效果：与现有技术相比，本发明具有下述优点：
(1)本发明提供的联苯合成方法，采用的廉价且低毒的氯化镁试剂，替代了毒性较大，价格昂贵的金属钯，铂等贵金属，符合环保的要求。
(2)氧化剂BQ可以直接购买，且价格低廉，避免了人工合成，节约了人力和财力。
(3)本发明提供的联苯类化合物具有结构简单，原料易得，反应条件温和，工艺简单，适合作为防污用途。
(4)本发明提供的4个联苯类化合物,比商业化的TBT具有更高的防污活性，且具有价格优势。
具体实施方式
以下结合实施例对本发明做进一步详细说明。所用试剂或者仪器设备未注明生产厂商的，均视为可以通过市场购买的常规产品。
实施例1
的合成工艺，步骤如下：
(1)向250mL三口烧瓶中加入20mL二氯乙烷和5.2g(0.03mol)2-溴-4-氟苯胺，室温下滴加3.1g(0.03mol)醋酸酐，20min滴加完毕。取样检测，得到中间体1(乙酰苯胺)，产率99％。
(2)室温下，将化合物2-溴-4-氟乙酰苯胺(3.7g,16mmol)和3,4-二氯溴苯(3.6g,16mmol)溶于THF(50mL)中，电磁搅拌，然后逐滴加入氯化镁试剂(4.9g，24mmol)，在50℃下反应2h。在另一个三颈烧瓶中，将加入FeBr 2 (1.16g,10mmol)于THF(50mL)中，搅拌30min后，将上述混合物加入此溶液中，继续反应20min后，加入氧化剂BQ(2.16g，20mmol)，室温下反应30min，将反应液经过一小段硅胶过滤，减压蒸馏，经柱层析得中间体2共3.23g,收率为68％。
(3)取一个1.0L的单口圆底烧瓶,向其中加入2.97g(10mmol)2-(3,4-二氯苯基)-4-氟乙酰苯胺，再向其中加入乙醇，充分溶解后，加入30mL浓盐酸。在90℃下回流3小时，利用TLC对反应进行跟踪，当原料彻底反应完后，停止反应，并趁热将混合液倒入到冰水中淬灭，得到中间体3，其为固体，共2.35g，收率为92％。
(4)制酰氯。制备方法如下：
首先准确称量对甲氧基苯甲酸0.27g(2mmol)于50mL的圆底烧瓶中，加入10mL无水二氯甲烷，随后用1mL注射器取0.31mL(4mmol)的氯化亚砜注入反应体系中，在设定为55℃的油浴锅中回流2h，用旋转蒸发仪除去氯化亚砜和二氯甲烷。
第二步：称取0.20g(0.78mmol,1equiv)中间体3，并用10mL无水二氯甲烷溶解，加入0.12mL(1.16mmol,1.5equiv)Et3N，将反应体系置于冰浴中。用10mL无水二氯甲烷与制好的酰氯混合均匀，缓慢的滴加至反应体系中，此时伴随白烟产生，随后在室温下反应2h，用TLC监测原料点是否消失。
加入3mL饱和碳酸氢钠溶液淬灭反应，搅拌10min，用二氯甲烷(30mL×3)萃取，饱和NaCl溶液洗涤，干燥、浓缩、层析柱纯化(石油醚∶乙酸乙酯＝4∶1)，得到化合物1，白色固体(0.27g,89％)。
化合物1.1H-NMR(400MHz,)δ8.20(dd,J＝9.0,5.3Hz,1H),8.20(dd,J＝9.0,5.3Hz,1H),7.63–7.57(m,2H),7.68–7.51(m,5H),7.57–7.52(m,2H),7.30–7.23(m,1H),7.28–7.24(m,1H),8.43–3.69(m,15H),7.13(ddd,J＝8.8,8.0,2.9Hz,1H),7.13(ddd,J＝8.8,8.0,2.9Hz,1H),6.99(dd,J＝8.7,2.9Hz,1H),6.99(dd,J＝8.7,2.9Hz,1H),6.97–6.86(m,2H),6.93–6.88(m,2H),3.85(s,3H),3.85(s,3H)。
(R＝基团1～20的产物)为联苯类杂环化合物，合成方法与上述方法相同，区别在于加入不同的酸，反应条件和性状如表1所示，鉴定如实施例2-20：
表1防污化合物的理化性质
实施例2
的鉴定
化合物2.1H-NMR(400MHz,)δ8.30–8.15(m,2H),8.39–8.09(m,2H),7.93(d,J＝8.1Hz,1H),8.02–7.76(m,2H),7.87(dd,J＝5.9,3.2Hz,1H),8.79–6.57(m,16H),7.50(ddd,J＝25.6,11.8,5.5Hz,8H),7.50(ddd,J＝25.6,11.8,5.5Hz,7H),7.22–7.13(m,1H),7.38–7.14(m,3H),7.14–6.94(m,1H),7.07–6.99(m,1H)。
实施例3
的鉴定
化合物3.1H-NMR(400MHz,)δ7.83(d,J＝7.6Hz,1H),7.83(d,J＝7.6Hz,1H),7.66(td,J＝7.4,0.8Hz,1H),7.66(td,J＝7.4,0.8Hz,1H),7.56(d,J＝7.5Hz,1H),7.50(d,J＝2.0Hz,1H),7.59–7.38(m,5H),7.47(d,J＝7.7Hz,1H),7.44–7.40(m,1H),8.22–6.22(m,14H),7.19(ddd,J＝5.7,3.7,2.1Hz,3H),7.19(ddd,J＝5.7,3.7,2.1Hz,2H),7.07–6.96(m,1H),7.06–6.97(m,1H),6.84(dd,J＝8.7,2.9Hz,1H),6.84(dd,J＝8.7,2.9Hz,1H),6.65(d,J＝11.0Hz,1H),6.65(d,J＝11.0Hz,1H)。
实施例4
的鉴定
化合物4.1H-NMR(400MHz,)δ8.40(d,J＝1.4Hz,1H),8.40(d,J＝1.4Hz,1H),8.11(d,J＝1.0Hz,1H),8.11(d,J＝1.0Hz,1H),8.00(dd,J＝8.7,5.2Hz,1H),8.00(dd,J＝8.7,5.2Hz,1H),7.85(s,1H),7.85(s,1H),7.55–7.51(m,1H),7.56–7.43(m,2H),8.77–6.62(m,10H),7.47(d,J＝1.8Hz,1H),7.22(dd,J＝8.2,2.0Hz,1H),7.22(dd,J＝8.2,2.0Hz,1H),7.16–7.09(m,1H),7.18–7.08(m,1H),7.02(dd,J＝8.6,2.9Hz,1H),7.02(dd,J＝8.6,2.9Hz,1H)。
实施例5
的鉴定
化合物5.1H-NMR(400MHz,)δ8.57(d,J＝2.0Hz,1H),8.57(d,J＝2.0Hz,1H),8.14(dd,J＝8.8,5.2Hz,1H),8.14(dd,J＝8.8,5.2Hz,1H),8.00(dd,J＝8.3,2.3Hz,1H),8.00(dd,J＝8.3,2.3Hz,1H),7.74(s,1H),7.74(s,1H),8.83–6.75(m,11H),7.55(d,J＝8.2Hz,1H),7.53(dd,J＝15.8,5.1Hz,2H),7.51(d,J＝1.9Hz,1H),7.43(d,J＝8.3Hz,1H),7.43(d,J＝8.3Hz,1H),7.26(s,1H),7.16(ddd,J＝8.8,8.0,2.9Hz,1H),7.16(ddd,J＝8.8,8.0,2.9Hz,1H),7.03(dd,J＝8.6,2.9Hz,1H),7.03(dd,J＝8.6,2.9Hz,1H)。
实施例6
的鉴定
化合物6.1H-NMR(400MHz,)δ9.71(s,1H),9.71(s,1H),9.31(d,J＝1.0Hz,1H),9.31(d,J＝1.0Hz,1H),8.47(dd,J＝9.1,5.3Hz,1H),8.47(dd,J＝9.1,5.3Hz,1H),8.30(d,J＝1.0Hz,1H),8.30(d,J＝1.0Hz,1H),7.56(dd,J＝5.2,3.0Hz,2H),7.56(dd,J＝5.2,3.0Hz,2H),10.31–2.21(m,12H),7.27(dd,J＝8.0,1.7Hz,1H),7.27(dd,J＝8.0,1.7Hz,1H),7.19–7.12(m,1H),7.21–7.11(m,1H),7.02(dd,J＝8.7,2.9Hz,1H),7.02(dd,J＝8.7,2.9Hz,1H),2.65(s,3H),2.65(s,3H)。
实施例7
的鉴定
化合物7.1H-NMR(400MHz,)δ9.76(s,1H),9.76(s,1H),9.47(d,J＝1.3Hz,1H),9.47(d,J＝1.3Hz,1H),8.77(d,J＝2.4Hz,1H),8.77(d,J＝2.4Hz,1H),8.49(dd,J＝9.1,5.3Hz,1H),8.53–8.43(m,2H),8.47–8.45(m,1H),10.20–6.37(m,11H),7.58(d,J＝5.4Hz,1H),7.61–7.54(m,2H),7.57(s,1H),7.28(dd,J＝8.3,2.1Hz,1H),7.32–7.24(m,2H),7.23–7.13(m,1H),7.22–7.14(m,1H),7.04(dd,J＝8.7,3.0Hz,1H),7.04(dd,J＝8.7,3.0Hz,1H)。
实施例8
的鉴定
化合物8.1H-NMR(400MHz,)δ8.59(s,1H),8.63–8.50(m,2H),8.55(d,J＝4.9Hz,1H),8.21(dd,J＝9.0,5.2Hz,1H),8.21(dd,J＝9.0,5.2Hz,1H),7.89(s,1H),7.89(s,1H),7.57(d,J＝4.9Hz,1H),7.61–7.48(m,3H),7.54(d,J＝8.2Hz,1H),8.91–6.86(m,11H),7.51(d,J＝2.1Hz,1H),7.23(dd,J＝8.2,2.1Hz,1H),7.29–7.13(m,3H),7.18(ddd,J＝8.9,7.9,2.9Hz,1H),7.01(dd,J＝8.6,2.9Hz,1H),7.01(dd,J＝8.6,2.9Hz,1H)。
实施例9
的鉴定
化合物9.1H-NMR(400MHz,)δ9.93(s,1H),9.93(s,1H),8.52(dd,J＝9.1,5.3Hz,1H),8.52(dd,J＝9.1,5.3Hz,1H),8.17–8.10(m,1H),8.18–8.10(m,1H),7.84(t,J＝7.8Hz,1H),7.84(t,J＝7.8Hz,1H),10.25–6.68(m,11H),7.63(d,J＝8.2Hz,1H),7.63(d,J＝8.2Hz,1H),7.55(d,J＝2.1Hz,1H),7.55(d,J＝2.1Hz,1H),7.49–7.43(m,1H),7.49–7.42(m,1H),7.31(dd,J＝8.2,2.0Hz,1H),7.34–7.23(m,2H),7.20–7.12(m,1H),7.21–7.11(m,1H),7.04(dd,J＝8.7,3.0Hz,1H),7.04(dd,J＝8.7,3.0Hz,1H)。
实施例10
的鉴定
化合物10.1H-NMR(400MHz,)δ9.96(s,1H),9.96(s,1H),8.08(dd,J＝4.6,1.2Hz,1H),8.08(dd,J＝4.6,1.2Hz,1H),7.86(dd,J＝7.7,1.5Hz,1H),7.86(dd,J＝7.7,1.5Hz,1H),7.72(d,J＝2.0Hz,1H),7.72(d,J＝2.0Hz,1H),7.64(d,J＝8.3Hz,1H),7.64(d,J＝8.3Hz,1H),10.33–6.31(m,13H),7.44(ddd,J＝10.3,8.5,3.8Hz,2H),7.51–7.25(m,4H),7.37–7.28(m,2H),6.93(s,2H),6.93(s,2H),6.60(dd,J＝7.7,4.8Hz,1H),6.60(dd,J＝7.7,4.8Hz,1H),2.50(s,3H)。
实施例11
的鉴定
化合物11.1H-NMR(400MHz,)δ8.65–8.59(m,1H),8.60(ddd,J＝9.8,7.6,2.0Hz,1H),8.59–8.36(m,2H),8.46(d,J＝14.9Hz,1H),8.34(ddd,J＝6.1,5.6,3.4Hz,3H),8.36–8.30(m,2H),9.12–6.30(m,14H),7.57(d,J＝8.2Hz,1H),7.57(d,J＝8.2Hz,1H),7.51(d,J＝2.0Hz,1H),7.51(d,J＝2.0Hz,1H),7.40(ddd,J＝7.4,4.8,2.4Hz,1H),7.40(ddd,J＝7.4,4.8,2.4Hz,1H),7.25(dd,J＝8.0,2.3Hz,2H),7.25(dd,J＝8.0,2.3Hz,2H),7.16(ddd,J＝9.0,8.0,3.0Hz,1H),7.16(ddd,J＝9.0,8.0,3.0Hz,1H),7.01(dd,J＝8.6,3.0Hz,1H),7.01(dd,J＝8.6,3.0Hz,1H)。
实施例12
的鉴定
化合物12.1H-NMR(400MHz,)δ8.44(dd,J＝4.7,1.9Hz,1H),8.44(dd,J＝4.7,1.9Hz,1H),8.23(dd,J＝9.0,5.2Hz,1H),8.23(dd,J＝9.0,5.2Hz,1H),8.11(dd,J＝7.7,1.9Hz,1H),8.11(dd,J＝7.7,1.9Hz,1H),8.83–6.60(m,11H),7.52(dd,J＝10.6,5.1Hz,2H),7.52(dd,J＝10.6,5.1Hz,2H),7.36(dd,J＝7.7,4.7Hz,1H),7.36(dd,J＝7.7,4.7Hz,1H),7.24(dd,J＝8.2,2.0Hz,1H),7.29–7.12(m,2H),7.20–7.14(m,1H),7.01(dd,J＝8.6,3.0Hz,1H),7.01(dd,J＝8.6,3.0Hz,1H)。
实施例13
的鉴定
化合物13.1H-NMR(400MHz,)δ8.41(d,J＝5.0Hz,1H),8.41(d,J＝5.0Hz,1H),8.04(dd,J＝8.9,5.2Hz,1H),8.04(dd,J＝8.9,5.2Hz,1H),7.93(s,1H),7.93(s,1H),7.59–7.51(m,2H),7.59–7.45(m,3H),7.48(d,J＝1.9Hz,1H),9.49–5.93(m,11H),7.35(d,J＝4.4Hz,1H),7.35(d,J＝4.4Hz,1H),7.22(dd,J＝8.2,1.9Hz,1H),7.29–7.09(m,2H),7.18–7.10(m,1H),7.07–6.99(m,1H),7.07–6.99(m,1H)。
实施例14
的鉴定
化合物14.1H-NMR(400MHz,)δ10.16(s,1H),10.16(s,1H),8.51(dd,J＝9.1,5.3Hz,1H),8.49(ddd,J＝6.7,5.1,4.4Hz,2H),8.46(dd,J＝3.0,2.1Hz,1H),8.24(d,J＝7.8Hz,1H),8.24(d,J＝7.8Hz,1H),7.88(td,J＝7.7,1.6Hz,1H),7.88(td,J＝7.7,1.6Hz,1H),10.50–6.66(m,12H),7.59(d,J＝2.1Hz,1H),7.62–7.53(m,2H),7.58–7.54(m,1H),7.44(ddd,J＝7.4,4.7,1.0Hz,1H),7.44(ddd,J＝7.4,4.7,1.0Hz,1H),7.30(dd,J＝8.2,2.2Hz,1H),7.34–7.23(m,2H),7.19–7.12(m,1H),7.21–7.10(m,1H),7.03(dd,J＝8.8,3.0Hz,1H),7.03(dd,J＝8.8,3.0Hz,1H)。
实施例15
的鉴定
化合物15.1H-NMR(400MHz,)δ10.43(s,1H),10.43(s,1H),8.99(s,1H),8.99(s,1H),8.86(d,J＝1.0Hz,1H),8.86(d,J＝1.0Hz,1H),11.20–6.08(m,11H),7.75(d,J＝1.9Hz,1H),7.78–7.59(m,4H),7.68(ddd,J＝8.4,6.2,3.5Hz,2H),7.63(d,J＝8.3Hz,1H),7.44(dd,J＝8.4,2.0Hz,1H),7.44(dd,J＝8.4,2.0Hz,1H),7.39–7.32(m,2H),7.40–7.30(m,2H),2.50(s,6H)。
实施例16
的鉴定
化合物16.1H-NMR(400MHz,)δ8.71(d,J＝1.2Hz,1H),8.71(d,J＝1.2Hz,1H),8.12(dd,J＝8.9,5.3Hz,1H),8.12(dd,J＝8.9,5.3Hz,1H),7.94(dd,J＝7.9,1.8Hz,2H),7.94(dd,J＝7.9,1.8Hz,2H),7.52(d,J＝8.2Hz,1H),7.51(dd,J＝8.8,5.1Hz,2H),7.50(d,J＝2.0Hz,1H),8.85–2.42(m,14H),7.28–7.25(m,1H),7.29–7.21(m,2H),7.24(d,J＝2.2Hz,1H),7.13(ddd,J＝8.9,8.2,3.0Hz,1H),7.13(ddd,J＝8.9,8.2,3.0Hz,1H),7.01(dd,J＝8.7,2.9Hz,1H),7.01(dd,J＝8.7,2.9Hz,1H),2.59(s,3H),2.59(s,3H)。
实施例17
的鉴定
化合物17.1H-NMR(400MHz,)δ8.31(d,J＝1.1Hz,1H),8.31(d,J＝1.1Hz,1H),8.19(d,J＝1.8Hz,1H),8.19(d,J＝1.8Hz,1H),7.87(s,1H),7.87(s,1H),7.78(dd,J＝8.9,5.3Hz,1H),7.78(dd,J＝8.9,5.3Hz,1H),7.58(s,1H),7.58(s,1H),7.24(d,J＝3.1Hz,1H),7.24(d,J＝3.1Hz,2H),8.68–1.88(m,14H),7.04–6.94(m,1H),7.02–6.96(m,1H),6.92–6.82(m,1H),6.91–6.83(m,1H),6.76(dd,J＝8.7,2.9Hz,1H),6.76(dd,J＝8.7,2.9Hz,1H),2.10(s,3H),2.10(s,3H)。
实施例18
的鉴定
化合物18.1H-NMR(400MHz,)δ8.79(s,1H),8.79(s,1H),8.62(d,J＝3.8Hz,1H),8.62(d,J＝3.8Hz,1H),8.21(s,1H),8.21(s,1H),8.00(d,J＝6.0Hz,2H),8.00(d,J＝6.0Hz,2H),7.48(d,J＝8.3Hz,1H),7.47(dd,J＝7.2,5.1Hz,2H),8.99–6.56(m,12H),7.47(d,J＝1.9Hz,1H),7.35(dd,J＝7.9,4.9Hz,1H),7.35(dd,J＝7.9,4.9Hz,1H),7.22(dd,J＝8.2,2.0Hz,1H),7.22(dd,J＝8.2,2.0Hz,1H),7.15–7.07(m,1H),7.16–7.05(m,1H),7.00(dd,J＝8.7,3.0Hz,1H),7.00(dd,J＝8.7,3.0Hz,1H)。
实施例19
的鉴定
化合物19.1H-NMR(400MHz,)δ11.41(s,1H),11.41(s,1H),8.69(dd,J＝7.3,2.1Hz,1H),8.69(dd,J＝7.3,2.1Hz,1H),8.38(dd,J＝9.1,5.4Hz,1H),8.38(dd,J＝9.1,5.4Hz,1H),11.66–6.34(m,10H),7.59(d,J＝2.0Hz,1H),7.59(d,J＝2.0Hz,1H),7.50(d,J＝8.2Hz,1H),7.50(d,J＝8.2Hz,1H),7.33(dd,J＝8.2,2.0Hz,1H),7.33(dd,J＝8.2,2.0Hz,1H),7.30–7.08(m,4H),7.20–7.09(m,2H),6.98(dd,J＝8.8,3.0Hz,1H),6.98(dd,J＝8.8,3.0Hz,1H),6.62(t,J＝6.7Hz,1H),6.62(t,J＝6.7Hz,1H)。
实施例20
的鉴定
化合物20.1H-NMR(400MHz,)δ8.60(d,J＝3.6Hz,2H),8.60(d,J＝3.6Hz,2H),8.23(s,1H),8.23(s,1H),8.03(dd,J＝8.9,5.2Hz,1H),8.03(dd,J＝8.9,5.2Hz,1H),7.50(d,J＝8.2Hz,1H),7.54–7.41(m,4H),7.46(t,J＝3.6Hz,3H),8.82–6.72(m,12H),7.29–7.17(m,1H),7.21(dd,J＝8.2,2.1Hz,1H),7.17–7.07(m,1H),7.16–7.09(m,1H),7.01(dd,J＝8.7,2.9Hz,1H),7.01(dd,J＝8.7,2.9Hz,1H)。
实施例21：实施例1～20所得化合物的防污活性测定
最小抑菌浓度(MIC)的测定方法
采用试管二倍稀释法，将合成的联苯类杂环化合物的浓度依次二倍稀释，然后将稀释菌液加入到联苯类杂环化合物稀释液中进行培养，大肠杆菌与金黄色葡萄球菌震荡培养24h，肉眼观察阳性对照管(不加受试化合物而接种菌的试管)有菌生长，出现混浊，阴性对照管(不加受试化合物也不接种菌的试管)无菌生长，呈现透明状态，以此确定待测物对2种试验菌株的最小抑菌浓度。据此判断，含联苯类杂环化合物对两种细菌的检测结果见表2。
表2化合物对2种菌的MIC
根据防污活性筛选，所合成的化合物均表现出了一定的防污活性，其中化合物2，化合物5，化合物8和化合物14表现出突出的防污活性，对金黄色葡萄球菌和大肠杆菌的MICs均达到了0.016mg/mL，优异于商品化的三丁基锡(TBT)防污剂。

Claims (8)

1.具有通式（I）的联苯类杂环化合物：
式（I）
所述的R为以下基团之任意一种:
。
2.权利要求1所述的具有通式（I）的联苯类杂环化合物的合成方法，其特征在于，反应式如下：
。
3.权利要求1所述的具有通式（I）的联苯类杂环化合物的合成方法，其特征在于，步骤如下：
（1）2-溴-4-氟苯胺与酸酐反应，发生酰化反应，生成所需要的酰胺化合物，目的是保护胺基，以免发生副反应；
（2）胺基保护产生的2-溴-4-氟乙酰苯胺，在氯化镁试剂以及溴化亚铁和氧化剂BQ的共同作用下，发生偶联反应；
（3）2-(3,4-二氯苯基)-4-氟乙酰苯胺发生水解反应，得到关键中间体，为联苯类化合物的合成提供了关键合成骨架；关键骨架2-(3,4-二氯苯基)-4-氟苯胺与不同的酸反应，生成20个目标化合物。
4.根据权利要求3所述的具有通式（I）的联苯类杂环化合物的合成方法，其特征在于，步骤（1）中，反应条件是：室温反应2~3 h。
5.根据权利要求3所述的具有通式（I）的联苯类杂环化合物的合成方法，其特征在于，步骤（2）中，所采用的有机溶剂选自***，四氢呋喃、二氧六烷、N,N-二甲基酰胺、丙酮、间二甲苯、二氯甲烷、二甲基乙酰胺中的任意一种；
加入氧化剂BQ的反应温度为 r.t ~ 50 ℃，反应时间20~90 min；
氯化镁试剂与氧化剂BQ的摩尔比为0.1~0.5:0.2~1.5。
6.根据权利要求3所述的具有通式（I）的联苯类杂环化合物的合成方法，其特征在于，步骤（3）中，所述的酸为以下杂环的酸的任意一种：对甲氧基苯甲酸，1-萘酸，3-氯异烟酸，5,6-二氯烟酸，异烟酸，5-甲基吡嗪-2-羧酸，2-羧酸吡嗪，5-氯吡嗪-2-羧酸，2-氯吡啶-6-羧酸，2-氨基烟酸，2-氟烟酸，2-氯烟酸，2-氯异烟酸，吡啶-2-羧酸，6-氯烟酸，6-甲基烟酸，5-甲基烟酸，烟酸，2-羟基烟酸或者邻醛基苯甲酸。
7.权利要求1所述的具有通式（I）的联苯类杂环化合物用于船舶防污的用途。
8.权利要求7所述用于船舶防污的用途，其特征在于，所涉及杀灭的菌类是金黄色葡萄球菌和大肠杆菌。
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