CN107141252A - 一种类水滑石材料催化含氮杂环化合物氧化脱氢的方法 - Google Patents

一种类水滑石材料催化含氮杂环化合物氧化脱氢的方法 Download PDF

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CN107141252A
CN107141252A CN201710492400.2A CN201710492400A CN107141252A CN 107141252 A CN107141252 A CN 107141252A CN 201710492400 A CN201710492400 A CN 201710492400A CN 107141252 A CN107141252 A CN 107141252A
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tetrahydroquinoline
containing heterocycle
heterocycle compound
houghite
nitrogen
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陶倩云
何明阳
周维友
潘九高
孙富安
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Changzhou University
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Abstract

本发明涉及一种以类水滑石为催化剂催化含氮杂环化合物氧化脱氢的方法，它属于类水滑石的应用方面。所述的类水滑石可表示为：An–‑M2+ xM3+‑LDHs(An–＝OH–或CO3 2–；M2+＝Ni，Co，Cu,Mg或Zn；M3+＝Fe，Mn，Al；M2+/M3+＝(2～4)。在所述催化剂存在下，不添加任何助剂，于温和条件下对杂环化合物进行氧化脱氢反应制备相应的芳香类化合物。本发明中的类水滑石材料基于非贵金属，可以大量合成，且可回收利用；此方法具有催化反应效率高，反应条件温和、成本低、易于工业化等优点。

Description

一种类水滑石材料催化含氮杂环化合物氧化脱氢的方法
技术领域
本发明属于类水滑石材料的应用领域，具体涉及一种以类水滑石材料为催化剂温和条件下催化含氮杂环化合物氧化脱氢的方法。
技术背景
含氮杂环化合物在有机化学中占据着非常重要的地位，其中含氮稠环杂环化合物是这类化合物中最引人关注的组成部分，由于含氮稠环杂环化合物通常具有独特的生物活性、低毒性和高内吸收性，经常用作医药活性分子和农药的结构单元。此外，含氮稠环杂环化合物在天然产物的合成、超导材料、储能材料、高分子材料以及有机染料等领域也有广泛应用。含氮杂环化合物的脱氢反应是非常重要的有机反应，也是合成相关含氮杂环化合物的重要方法之一。
目前用于含氮杂环化合物脱氢反应的催化体系主要包括Pd，Au，Ru，Fe，Cu，Ir及Pt等，这些体系存在着以下缺点：(1)采用贵金属作为活性中心；(2)金属络合物催化剂的配体合成复杂；(3)反应条件苛刻，如需要高温和高压条件；(4)基于非贵金属的非均相催化剂制备过程复杂。上述不足限制了含氮杂环化合物的脱氢反应的广泛应用。Kankana Mullick等(Chem.Commun.,2017,53,2256-2259)以介孔氧化锰为催化剂，空气为氧化剂实现了部分含氮杂环化合物的脱氢反应，但是催化剂的效率过低，转化频率只有0.07h-1。因此，基于廉价易得的材料开发高效的催化体系，用于实现温和条件下的含氮杂环化合物的高效氧化脱氢反应非常必要。本发明旨在开发一种以类水滑石为催化剂高效催化含氮杂环化合物在分子氧条件下氧化脱氢的方法。我们发明了非均相廉价无毒，制备简单的类水滑石催化剂，更加绿色且条件温和，具有很好的应用前景。
发明内容
本发明的目的是提供一种以类水滑石为催化剂催化含氮杂环化合物有效氧化脱氢的方法。此方法具有催化剂制备简单、反应高效、反应操作简单等特点。
催化含氮杂环化合物氧化脱氢反应的步骤：在液相条件下，有机溶剂中，以类水滑石为催化剂，含氧气体为氧化剂，对含氮杂环化合物进行氧化脱氢反应制得芳香化合物；反应温度为80～120℃。
本发明的反应中，所述类水滑石催化剂可表示为：An–-M2+ xM3+-LDHs(An–＝OH–或CO3 2–；M2+＝Ni，Co， Cu,Mg或Zn；M3+＝Fe，Mn，Al；M2+/M3+＝(2～4)；
本发明的反应中，反应的溶剂为1,3,5-三甲苯、N,N二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、三氟甲苯、苯甲腈、乙腈、二氧六环；
本发明相对于现有技术具有如下优点及效果：
(1)本发明所提供的用于含氮杂环化合物氧化脱氢的方法，采用非均相催化体系，在温和条件下即可实现目标化合物的高效合成。解决了温和条件下需要贵金属及复杂配体的问题。
(2)本发明所述催化反应方法具有良好的底物适用性，可以高效催化各种含氮杂环化合物反应生成对应的芳香化合物。
附图说明
图1～3为催化剂样品的结构通过其X射线衍射图。采用日本理学D/max 2500PC型号的X-光衍射仪对催化剂样品表征。CuKα射线，工作电压40kV，电流100mA，衍射角2θ为5°～80°，扫描速率 12°/min。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
本发明所述用于含氮杂环化合物的氧化脱氢的催化剂An–-M2+ xM3+-LDHs，可按照如下实施例1～9制备：
实施例1
准确称量1.6g的氢氧化钠溶液，加入2.8g的氨水，充分搅拌均匀，用去离子水溶解定容至200mL；称取9.305g的硝酸镍和2.013g氯化锰溶解定容至200mL，并将上述混合碱溶液倒入三口烧瓶中，用恒压分液漏斗将上述混合盐溶液缓慢滴加到三口烧瓶中，控制搅拌的速度为350r/min。滴加过程中保持温度为 30℃，当滴加完成后，控制温度为50℃静置24h，冷却至室温；将冷却的混合溶液用去离子水洗涤至中性，然后抽滤，在70℃下干燥，研磨成粉末状，制备得到OH–-Ni2Mn-LDH。
实施例2
准确称量7.1g的氨水，充分搅拌均匀，用去离子水溶解定容至100mL；称取1.94g的硝酸钴和3.8g 硝酸镍溶解定容至100mL，并将上述氨水溶液倒入四口烧瓶中，通入氧气，在35℃的条件下用恒压分液漏斗将上述混合盐溶液缓慢滴加到四口烧瓶中，控制滴加最终的pH值为8.5～9.0，控制搅拌的速度为350 r/min。滴加过程中保持温度为30℃，当滴加完成后，控制温度为35℃通氧气静置24h，冷却至室温；将冷却的混合溶液用去离子水洗涤至中性，然后抽滤，在70℃下干燥，研磨成粉末状，制备得到 OH–-Ni2Co-LDH。
实施例3
准确称量9.34g的氢氧化钠溶液，加入9.632g的氨水，充分搅拌均匀，用去离子水溶解定容至200mL；称取20g的硝酸镍和6.9387g硝酸铁溶解定容至200mL，并将上述混合碱溶液倒入三口烧瓶中，用恒压分液漏斗将上述混合盐溶液缓慢滴加到三口烧瓶中，控制搅拌的速度为350r/min。滴加过程中保持温度为 25℃，当滴加完成后，控制温度为25℃静置48h，冷却至室温；将冷却的混合溶液用去离子水洗涤至中性，然后抽滤，在70℃下干燥，研磨成粉末状，制备得到OH–-Ni2Fe-LDH。
实施例4
准确称量6.4g的氢氧化钠溶液，加入7.1g的氨水，充分搅拌均匀，用去离子水溶解定容至200mL；称取11.63g的硝酸镍和8g硝酸铬溶解定容至60mL，用恒压分液漏斗将上述混合盐溶液和混合碱溶液缓慢滴加到三口烧瓶中，并且控制滴加过程中的PH值为7.5左右。控制搅拌的速度为350r/min。滴加过程中保持温度为70℃，当滴加完成后，控制温度为70℃静置12h，冷却至室温；将冷却的混合溶液用去离子水洗涤至中性，然后抽滤，在70℃下干燥，研磨成粉末状，制备得到OH–-Ni2Cr-LDH。
实施例5
准确称量2.65g的碳酸钠和16g氢氧化钠用去离子水搅拌溶解定容至125mL；称取28.98g的硝酸铜和8.72g硝酸镍和18.75g的硝酸铝溶解定容至125mL,并将上述碱混合溶液倒入三口烧瓶中，用恒压分液漏斗将上述混合盐溶液缓慢滴加到三口烧瓶中，控制搅拌的速度为350r/min。当滴加完成后，控制温度为 50℃静置4h，冷却至室温；将冷却的混合溶液用去离子水洗涤至中性，然后抽滤，在70℃下干燥，研磨成粉末状，制备得到CO3 2–-CuNiAl-LDH。
实施例6
准确称量10.6g的碳酸钠用去离子水搅拌溶解定容至100mL，称量13.2g的氢氧化钠搅拌溶解定容至 100mL；称取12.07g的硝酸铜和12.8g硝酸镁和18.75g的硝酸铝溶解定容至150mL,并将上述碳酸钠溶液倒入四口烧瓶中，用恒压分液漏斗将上述氢氧化钠溶液和上述混合盐溶液缓慢滴加到四口烧瓶中，在滴加的过程中控制pH值为10左右，控制搅拌的速度为350r/min。当滴加完成后，控制温度为60℃静置14 h，冷却至室温；将冷却的混合溶液用去离子水洗涤至中性，然后抽滤，在70℃下干燥，研磨成粉末状，制备得到CO3 2–-CuMgAl-LDH。
实施例7
准确称量10.6g的碳酸钠用去离子水搅拌溶解定容至100mL，称量13.2g的氢氧化钠搅拌溶解定容至 100mL；取12.07g的硝酸铜和7.42g硝酸锌和8.75g的硝酸铝溶解定容至150mL，并将上述碳酸钠溶液倒入四口烧瓶中，用恒压分液漏斗将上述氢氧化钠溶液和上述混合盐溶液缓慢滴加到四口烧瓶中，在滴加的过程中控制pH值为10左右，控制搅拌的速度为350r/min。当滴加完成后，控制温度为60℃静置15h，冷却至室温；将冷却的混合溶液用去离子水洗涤至中性，然后抽滤，在70℃下干燥，研磨成粉末状，制备得到CO3 2–-CuZnAl-LDH。
实施例8
准确称量1.6g的氢氧化钠溶液，加入2.8g的氨水，充分搅拌均匀，用去离子水溶解定容至200mL；称取9.519g的硝酸锌和2.013g氯化锰溶解定容至200mL，并将上述混合碱溶液倒入三口烧瓶中，用恒压分液漏斗将上述混合盐溶液缓慢滴加到三口烧瓶中，控制搅拌的速度为350r/min。滴加过程中保持温度为 30℃，当滴加完成后，控制温度为50℃静置24h，冷却至室温；将冷却的混合溶液用去离子水洗涤至中性，然后抽滤，在70℃下干燥，研磨成粉末状，制备得到OH–-Zn2Mn-LDH。
实施例9
准确称量4g的氢氧化钠用去离子水溶解定容至100mL，准确称量7.1g的氨水用去离子水溶解定容至100mL；称取11.63g的硝酸镍和7.5g氯化铝溶解定容至100mL，并将上述碳酸钠溶液倒入四口烧瓶中，用恒压分液漏斗将上述氢氧化钠溶液和上述混合盐溶液缓慢滴加到四口烧瓶中，在滴加的过程中控制 pH值为10左右，控制搅拌的速度为350r/min。当滴加完成后，控制温度为40℃静置24h，冷却至室温；将冷却的混合溶液用去离子水洗涤至中性，然后抽滤，在70℃下干燥，研磨成粉末状，制备得到 CO3 2–-Ni2Al-LDH。。
本发明所述以类水滑石为催化剂催化含氮杂环化合物方法可以通过实施例10～16来说明：
实施例10不同类水滑石催化剂的催化活性
典型反应步骤如下：将80mg的类水滑石催化剂，0.5mmol四氢喹啉和2mL 1,3,5-三甲苯溶剂加入反应器中，常压反应，温度120℃，在氧气的氛围下，反应时间2.5h，采用气相色谱内标法(硝基苯作内标)分析液体中原料四氢喹啉和产物喹啉的含量，计算反应的转化率和选择性。反应结果见表1。
表1 不同类水滑石催化剂的催化反应结果
由表1可见，在常压条件下，含Ni、Mn、Co及Cu类水滑石在含氮杂环化合物的氧化脱氢反应中具有优异的催化活性。以OH–-Ni2Mn-LDH为催化剂时，四氢喹啉的在2.5h内转化完全，脱氢产物喹啉的选择性为93.2％。与对比结果相比，本发明的催化体系具有明显优势。
实施例11不同溶剂条件下的反应结果
将80mg OH–-Ni2Mn-LDH催化剂，0.5mmol四氢喹啉和2mL溶剂加入反应器中，常压反应，温度 100℃，在氧气的氛围下，反应时间12h，采用气相色谱内标法(硝基苯作内标)分析液体中原料四氢喹啉和产物喹啉的含量，计算反应的转化率和选择性。反应结果见表2。
表2 不同溶剂下四氢喹啉氧化脱氢反应结果
实施例12
将80mg OH–-Ni2Mn-LDH类水滑石催化剂，0.5mmol四氢喹啉和2mL 1,3,5-三甲苯溶剂加入反应器中，常压反应，温度80℃，在氧气的氛围下，反应时间2.5h，采用气相色谱内标法(硝基苯作内标)分析液体中原料四氢喹啉和产物喹啉的含量。反应的转化率为83.3％，选择性56.3％。
实施例13
将80mg Ni2Mn-LDH类水滑石催化剂，0.5mmol四氢喹啉和2mL 1,3,5-三甲苯溶剂加入反应器中，常压反应，温度120℃，在氧气的氛围下，反应时间2.5h，采用气相色谱内标法(硝基苯作内标)分析液体中原料四氢喹啉和产物喹啉的含量。四氢喹啉的转化率＞99％，反应的选择性为93.1％。
实施例14
将50mg Ni2Mn-LDH类水滑石催化剂，0.5mmol四氢喹啉和2mL 1,3,5-三甲苯溶剂加入反应器中，常压反应，温度120℃，在氧气的氛围下，反应时间2.5h，采用气相色谱内标法(硝基苯作内标)分析液体中原料四氢喹啉和产物喹啉的含量，计算反应的转化率和选择性。四氢喹啉的转化率为89.3％，反应的选择性为67.9％。
实施例15
将200mg Ni2Mn-LDH类水滑石催化剂，0.5mmol四氢喹啉和2mL 1,3,5-三甲苯溶剂加入反应器中，常压反应，温度80℃，在氧气的氛围下，反应时间2.5h，采用气相色谱内标法(硝基苯作内标)分析液体中原料四氢喹啉和产物喹啉的含量，计算反应的转化率和选择性。四氢喹啉的转化率＞99％，反应的选择性78.3％。
实施例16 此方法在其它含氮杂环化合物氧化脱氢反应中的应用
表3 不同反应底物的氧化反应结果
以上实例仅用于说明本发明的内容，除此之外，本发明还有其它实施方式。但是凡采用等同替换或等效变形方式形成的技术方案均落在本发明的保护范围内。

Claims (5)

1.一种以类水滑石为催化剂高效催化分子氧氧化脱氢含氮杂环化合物的方法，其特征在于类水滑石氧化脱氢含氮杂环化合物的具体做法如下，在液相条件下，有机溶剂中，以类水滑石为催化剂，含氧气体为氧化剂，对含氮杂环化合物进行氧化脱氢反应制得相应的芳香化合物。
2.根据权利要求1所述的类水滑石氧化脱氢含氮杂环化合物的方法，其特征在于所述的类水滑石可表示为：An–-M2+ xM3+-LDHs(An–＝OH–或CO3 2–；M2+＝Ni，Co，Cu,Mg或Zn；M3+＝Fe，Mn，Al；M2+/M3+＝(2～4)。
3.根据权利要求1-2所述的类水滑石氧化脱氢含氮杂环化合物的方法，其特征在于所述的反应温度为80～120℃。
4.根据权利要求1-2所述的类水滑石氧化脱氢含氮杂环化合物的方法，其特征在于所述的溶剂为1,3,5-三甲苯、N,N二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、三氟甲苯、苯甲腈、乙腈、二氧六环。
5.根据权利要求1所述的类水滑石氧化脱氢含氮杂环化合物的方法，其特征在于所述的含氮杂环化合物为四氢喹啉、2-甲基四氢喹啉、3-甲基四氢喹啉、4-甲基四氢喹啉、6-甲基四氢喹啉、8-甲基四氢喹啉、6-氟四氢喹啉、6-氯四氢喹啉、6-溴四氢喹啉、6-甲氧基四氢喹啉、2,6-二甲基四氢喹啉、吲哚啉、喹喔啉、2,3-二甲基喹喔啉、7-甲基四氢喹啉、7,8-苯并喹啉，2-甲基-6甲氧基四氢喹啉、异喹啉等。
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