CN108610330B - 一种氯代吡啶基桥联双四唑化合物及其合成和应用 - Google Patents
一种氯代吡啶基桥联双四唑化合物及其合成和应用 Download PDFInfo
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Abstract
本发明公开了一种氯代吡啶基桥联双四唑化合物及其合成和应用。在加热条件下，吡啶基桥联双酰胺化合物在五氯化磷及二氯亚砜作用下生成氯代吡啶基桥联双亚胺酰氯化合物，该化合物再与叠氮化钠发生缩合反应得到氯代吡啶基桥联双四唑化合物。该化合物可用于合成高效过渡金属催化剂。本发明具有原料廉价易得、操作简便、合成反应条件温和等优点。
Description
技术领域
本发明涉及一种氯代吡啶基桥联双四唑化合物及其合成和应用。以吡啶基桥联双酰胺化合物为原料，在五氯化磷及二氯亚砜作用下生成氯代吡啶基桥联双亚胺酰氯化合物，该化合物再与叠氮化钠发生缩合反应得到氯代吡啶基桥联双四唑化合物。该化合物可用于合成高效过渡金属催化剂。本发明具有原料廉价易得、操作简便、合成反应条件温和等优点。
技术背景
四唑类化合物及其衍生物具有高含氮量、高生成焓及稳定性好等特点，在生物化学、农业、功能材料学及配位化学等方面有着广泛的应用。四唑类化合物可与生物体内多种酶和受体相互作用而呈现出广泛的生物活性，目前已有较多四唑类化合物应用于临床，如抗血压类药物奥美沙坦酯、抗生素药物头孢哌酮等。在农业领域，四唑类化合物在除草和植物生长调节方面也取得了许多重要的研究成果，如除草剂四唑嘧磺隆。在材料领域，四唑类化合物广泛用于起爆药、固体推进剂等含能材料的制备。四唑类化合物还可以作为催化剂用于催化多种反应，如Heck、Suzuki等偶联反应。对四唑类化合物进行适当的官能团化具有十分重要的意义。
氯代吡啶基桥联的双四唑化合物即保留了四唑基团，又具有含氮三齿配体独特的钳形结构，可用于制备金属有机材料或高活性配合物催化剂。本发明以易于制备的吡啶基桥联双酰胺化合物为原料，在五氯化磷及二氯亚砜作用下生成氯代吡啶基桥联双亚胺酰氯化合物，该化合物再与叠氮化钠发生缩合反应得到氯代吡啶基桥联双四唑化合物。
发明内容
本发明的目的在于提供一种原料廉价易得、操作简便、反应条件温和的合成氯代吡啶基桥联双四唑化合物的方法及其应用。
为了实现上述目的，本发明的技术方案如下：吡啶基桥联双酰胺化合物2在五氯化磷及二氯亚砜作用下得到氯代吡啶基桥联双亚胺酰氯化合物3，3与叠氮化钠发生缩合反应，反应结束后按常规分离纯化方法进行产物分离和表征，得到氯代吡啶基桥联双四唑化合物1。
技术方案的特征在于：
1、吡啶基桥联双酰胺化合物2为合成子，其中取代基R为氢、甲基、乙基、甲氧基、氯或溴。
2、吡啶基桥联双酰胺化合物2与五氯化磷的摩尔比为1:2-1:5；五氯化磷与二氯亚砜的摩尔比为1:5-1:20；吡啶基桥联双酰胺化合物2与五氯化磷及二氯亚砜反应的温度为50-79℃；反应时间为1-12小时。
3、氯代吡啶基桥联双亚胺酰氯化合物3与叠氮化钠的摩尔比为1:2-1:5。反应溶剂可为二甲基亚砜、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺；反应温度为-20-30℃；反应时间为0.1-12小时。
本发明具有以下优点：
1)氯代吡啶基桥联双四唑化合物1之前没有文献报道。
2)反应原料来源广泛，便宜易得或者易于制备。
3)氯代吡啶基桥联双四唑化合物1用途较广，可用于制备高活性配合物催化剂或配合物发光材料。
总之，本发明以吡啶基桥联双酰胺化合物2为原料，经氯代，再与叠氮化钠缩合反应高效合成用途广泛的氯代吡啶基桥联双四唑化合物1，合成方法简便，反应条件温和。
具体实施方式
本发明以吡啶基桥联双酰胺化合物2为起始原料，经氯代，再与叠氮化钠缩合反应合成氯代吡啶基桥联双四唑化合物1。通过下述实施例有助于进一步理解本发明，但本发明的内容并不限于此。
实施例1
吡啶基桥联双酰胺化合物2a((20.0g,58mmol)，PCl5(26.7g,128mmol)，SOCl2(120mL)在70℃搅拌反应8小时。蒸馏除去过量的二氯亚砜，将生成的氯代吡啶基桥联双亚胺酰氯化合物3a溶于80mL二甲基亚砜。反应液冷至室温，再滴加到NaN3(15.1g,232mmol)/二甲基亚砜(100mL)中，滴完后室温继续反应5小时。
反应结束后，加入200mL水处理，分层，有机相3×200mL水洗，除去溶剂后溶于二氯甲烷，硅胶柱层析分离，洗脱液为石油醚(60-90℃)/乙酸乙酯(v/v，5:1)。收集含目标产物的洗脱液并减压(20mmHg)除去溶剂，得目标产物氯代吡啶基桥联双四唑化合物1a(11.5g，收率46％)，其结构通过1H,13C NMR,HRMS测试得到确认。1H NMR(CDCl3,400MHz,23℃)δ8.28(s,2H),7.11and(d each,4:4H),2.38(s,6H).13C{1H}NMR(CDCl3,100MHz,23℃)δ150.7,147.1,145.8,140.6,131.8,129.8,127.2,124.8,21.4.HRMS calcd.for C21H16ClN9:429.1217；Found:429.1212。
实施例2
吡啶基桥联双酰胺化合物2b(2.1g,5mmol)，PCl5(4.2g,20mmol)，SOCl2(30mL)在50℃搅拌反应12小时。蒸馏除去二氯亚砜，将生成的氯代吡啶基桥联双亚胺酰氯化合物3b溶于15mL N,N-二甲基甲酰胺。反应液冷至室温，再滴加到NaN3(15.1g,10mmol)/N,N-二甲基甲酰胺(10mL)中，滴加时控制反应温度为0-5℃，滴完后0-5℃继续反应12小时。
反应结束后，加入20mL水处理，分层，有机相3×20mL水洗，除去溶剂后溶于二氯甲烷，硅胶柱层析分离，洗脱液为石油醚(60-90℃)/乙酸乙酯(v/v，5:1)。收集含目标产物的洗脱液并减压(20mmHg)除去溶剂，得目标产物氯代吡啶基桥联双四唑化合物1b(1.2g，收率51％)，其结构通过1H,13C NMR,HRMS测试得到确认。1H NMR(CDCl3,400MHz,23℃)δ8.29(s,2H),7.13and 6.95(d each,4:4H).13C{1H}NMR(CDCl3,100MHz,23℃)δ151.9,149.2,143.1,138.7,130.2,129.5,126.2,125.1.HRMS calcd.for C19H10Cl3N9:469.0125；Found:469.0121。
应用例1
在氮气保护下，25mL Schlenk反应瓶中依次加入配体1a(215mg,0.5mmol)、RuCl2(PPh3)3(480mg,0.5mmol)和40mL二氯甲烷，回流反应4h。冷至室温后，除去溶剂后，硅胶柱层析分离，洗脱液为二氯甲烷/甲醇(v/v，10:1)。收集含目标产物的洗脱液并减压(20mmHg)除去溶剂，得目标产物4a(479mg，收率85％)。其结构通过NMR与HRMS测定得到确认。
在氮气保护下，把苯乙酮(2.0mmol)，加入0.5mol％催化剂4a，18mL异丙醇在82℃搅拌5分钟。然后将2.0mL iPrOK的异丙醇溶液(0.1M)注入反应体系中，在指定的时间内，抽取0.1mL的反应液，并立即用0.5mL异丙醇稀释后做气相色谱分析。在所述条件下，1h时苯乙酮以97％的转化率还原为对应的醇产物，说明本发明的氯代吡啶基桥联双四唑化合物可作为潜在的酮还原催化剂使用。
Claims (8)
1.一种氯代吡啶基桥联双四唑化合物，其结构式1如下式 所示，
取代基R为氢、甲基、乙基、甲氧基、氯或溴。
2.一种权利要求1所述氯代吡啶基桥联双四唑化合物的合成方法，其特征在于：以吡啶基桥联双酰胺化合物2为原料，在五氯化磷及二氯亚砜作用下得到氯代吡啶基桥联双亚胺酰氯化合物3，化合物3与叠氮化钠经缩合反应得到氯代吡啶基桥联双四唑化合物1；合成路线如下述反应式所示：
其中，吡啶基桥联双酰胺化合物2的结构如下，
取代基R为氢、甲基、乙基、甲氧基、氯或溴。
3.按照权利要求2所述的合成方法，其特征在于：吡啶基桥联双酰胺化合物2与五氯化磷的摩尔比为1:2-1:5；五氯化磷与二氯亚砜的摩尔比为1:5-1:20。
4.按照权利要求2所述的合成方法，其特征在于：吡啶基桥联双酰胺化合物2与五氯化磷及二氯亚砜反应的温度为50-79 ºC；反应时间为1-12小时。
5.按照权利要求2所述的合成方法，其特征在于：氯代吡啶基桥联双亚胺酰氯化合物3与叠氮化钠的摩尔比为1:2-1:5。
6.按照权利要求2所述的合成方法，其特征在于：氯代吡啶基桥联双亚胺酰氯化合物3与叠氮化钠反应的溶剂为二甲基亚砜、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺，溶剂的用量为：1 mmol原料氯代吡啶基桥联双亚胺酰氯化合物3使用溶剂0.5-10 mL。
7.按照权利要求2所述的合成方法，其特征在于：氯代吡啶基桥联双亚胺酰氯化合物3与叠氮化钠反应的温度为-20-30 ºC；反应时间为0.1-12小时。
8.一种权利要求1所述氯代吡啶基桥联双四唑化合物在用于酮还原的金属配合物催化剂中的应用。
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