CN106831563A - 一种碳氮材料催化含氮杂环氧化脱氢制备喹啉衍生物的方法 - Google Patents

一种碳氮材料催化含氮杂环氧化脱氢制备喹啉衍生物的方法 Download PDF

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CN106831563A
CN106831563A CN201510886033.5A CN201510886033A CN106831563A CN 106831563 A CN106831563 A CN 106831563A CN 201510886033 A CN201510886033 A CN 201510886033A CN 106831563 A CN106831563 A CN 106831563A
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carbon
nitrogen
heterocyclic ring
quinoline
nitrogen material
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CN106831563B (zh
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高爽
陈波
王连月
吕迎
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/18—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms

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Abstract

本发明属于化学合成领域，具体涉及一种碳氮材料催化含氮杂环氧化脱氢制备喹啉衍生物的方法。该碳氮材料以含氮有机大环化合物为前驱体，在惰性氛围焙烧制得。反应以氧气或空气为氧化剂，在有或无溶剂下，50～120℃反应，碳氮材料即可将含氮杂环转化成对应的喹啉衍生物。本发明反应体系无任何金属引入，易放大，且催化剂回收循环使用至少9次依旧保持很好的选择性和活性，具有显著的工业生产实用前景。

Description

一种碳氮材料催化含氮杂环氧化脱氢制备喹啉衍生物的方法
技术领域
本发明属于化学合成领域，具体涉及一种碳氮材料催化含氮杂环氧化脱氢制备喹啉衍生物的方法。
背景技术
喹啉衍生物是一种重要的中间体，在有机、药物、天然产物和工业合成中都具有极其重要的应用。目前报道的含氮杂环氧化脱氢制备喹啉衍生物的催化剂有：1)均相金属催化剂(Rh、Ir、Pt、Os等)；2)多相金属催化剂(Rh、Pd、Pt、Au、Ni、Co、Fe等)。但这些体系存在以下一种或多种的缺陷和不足：1)金属催化尤其是均相催化体系，对于产物特别是医药类药物的纯化带来很大困难；2)贵金属存在价格昂贵稀缺等弊端；3)助剂的添入，例如无机碱等，也会带来额外的废弃物。因此无论是从实验室研究还是工业应用角度来说，发展一类高效，廉价，绿色的催化剂对喹啉衍生物的合成具有重要的意义。
发明内容
本发明的目的是为了克服现有技术催化体系存在的缺点，提供一类高效的碳氮材料催化氮杂环氧化脱氢制备喹啉衍生物的方法。本发明催化剂制备简单，高效稳定，反应条件温和，产率高。
本发明所涉及的反应可以用以下通式来表示：
底物含氮杂环包含取代的1,2,3,4-四氢喹啉类化合物，其中取代基R1，R2可为芳基、卤素、硝基、烷氧基、烷基或氢原子。
催化剂以有机大环化合物(包括酞菁、卟啉化合物)为前驱体，在200～1000℃惰性气氛(N2或Ar)焙烧即可获得。
在反应中，加入相对于底物的质量分数为0～100％的催化剂，温度控制在50～120℃，以空气或氧气作为氧化剂，反应1～48h即可获得相应的喹啉类目标产物。
具体实施方式
以下实施方式有助于理解本发明，但并不限制于本发明内容。
实施例1
以酞菁为前驱体，在800℃氮气氛围焙烧2h，自然冷却室温后，即可获得所需催化剂。在Schlenk瓶中加入0.5mmol的1,2,3,4-四氢喹啉，20mg的催化剂，氧气球为氧源，在100℃下搅拌反应12h，得到相应的目标产物，收率为88％。
实施例2
碳材料制备如实例1所述，在Schlenk瓶中加入0.5mmol的6-甲氧基-1,2,3,4-四氢喹啉，20mg催化剂，氧气球为氧源，在100℃下搅拌反应12h，得到相应的目标产物，收率为90％。
实施例3
碳材料制备如实例1所述，在Schlenk瓶中加入0.5mmol的6-甲基-1,2,3,4-四氢喹啉，20mg催化剂，氧气球为氧源，在100℃下搅拌反应12h，得到相应的目标产物，收率为88％。
实施例4
碳材料制备如实例1所述，在Schlenk瓶中加入0.5mmol的6-氯-1,2,3,4-四氢喹啉，20mg催化剂，氧气球为氧源，在100℃下搅拌反应12h，得到相应的目标产物，收率为85％。
实施例5
碳材料制备如实例1所述，在Schlenk瓶中加入0.5mmol的6-硝基-1,2,3,4-四氢喹啉，20mg催化剂，氧气球为氧源，在100℃下搅拌反应12h，得到相应的目标产物，收率为80％。
实施例6
碳材料制备如实例1所述，在Schlenk瓶中加入0.5mmol的2-甲基-1,2,3,4-四氢喹啉，20mg催化剂，氧气球为氧源，在100℃下搅拌反应12h，得到相应的目标产物，收率为82％。
实施例7
碳材料制备如实例1所述，在Schlenk瓶中加入0.5mmol的3-甲基-1,2,3,4-四氢喹啉，20mg催化剂，氧气球为氧源，在100℃下搅拌反应12h，得到相应的目标产物，收率为79％。
实施例8
碳材料制备如实例1所述，在Schlenk瓶中加入0.5mmol的4-甲基-1,2,3,4-四氢喹啉，20mg催化剂，氧气球为氧源，在100℃下搅拌反应12h，得到相应的目标产物，收率为82％。
实施例9
催化剂制备如实例1所述，在Schlenk瓶中加入0.5mmol的1,2,3,4-四氢苯并[h]喹啉，20mg碳氮材料，氧气球为氧源，在100℃下搅拌反应8h，得到相应的目标产物，收率为67％。

Claims (8)

1.一种碳氮材料催化含氮杂环氧化脱氢制备喹啉衍生物的方法，其特征在于，该方法包括：以含氮杂环为底物，碳氮材料为催化剂，氧气或空气为氧化剂，在有溶剂或无溶剂下，即可将底物转化为相应的喹啉衍生物，其反应通式如下：
其中取代基R1，R2可分别为芳基、卤素、硝基、C1－C10的烷基或烷氧基、或氢原子。
2.根据权利要求1所述的方法，其特征在于，底物为取代的1,2,3,4-四氢喹啉化合物。
3.根据权利要求1所述的方法，其特征在于，所述的碳氮材料以有机大环为前驱体，包括酞菁、或卟啉中的一种或二种以上，在200～1000℃的N2或Ar氛围焙烧制备而成。
4.根据权利要求1所述的方法，其特征在于，所使用氧化剂的压力为0.01～5MPa。
5.根据权利要求1所述的方法，其特征在于，催化剂加入量相对于底物的质量分数为0.1～100％。
6.根据权利1所述方法，其特征在于，反应溶剂为甲醇、乙醇、芳香烃、烷烃(5～12个碳原子)中的一种。
7.根据权利1所述方法，其特征在于，反应温度在50～120℃。
8.根据权利1所述方法，其特征在于，芳基为苯基或取代苯基，苯基上的取代基为氢、羟基、C1-C10的烷基或烷氧基、氨基、硝基或卤素中的一种或二种以上，取代基个数为1-5个。
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Cited By (7)

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CN107141252A (zh) * 2017-06-26 2017-09-08 常州大学 一种类水滑石材料催化含氮杂环化合物氧化脱氢的方法
CN107353245A (zh) * 2017-08-24 2017-11-17 福州大学 一种喹啉类化合物的合成方法
CN107376970A (zh) * 2017-07-25 2017-11-24 中国石油大学(北京) 单原子铁掺氮多孔碳催化剂及其制备方法与应用
CN109529907A (zh) * 2018-12-30 2019-03-29 中南民族大学 一种氮掺杂碳材料负载钴催化剂及其制备方法和在n-杂环化合物催化氧化中的应用
CN113024458A (zh) * 2019-12-09 2021-06-25 中国科学院大连化学物理研究所 一种生物质基碳材料实现含氮杂环氧化脱氢的方法
CN113929610A (zh) * 2021-11-17 2022-01-14 甘肃警察职业学院 一种基于离子液体多孔碳材料催化氮杂环需氧脱氢的方法
CN116272943A (zh) * 2023-03-24 2023-06-23 遵义医科大学 一种碳基非金属催化剂及其制备方法和应用

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CN101041634A (zh) * 2006-03-23 2007-09-26 中国科学院上海药物研究所 3－取代喹啉衍生物及其合成方法
CN102558046A (zh) * 2012-01-18 2012-07-11 云南大学 喹啉化合物的固相合成方法

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CN101041634A (zh) * 2006-03-23 2007-09-26 中国科学院上海药物研究所 3－取代喹啉衍生物及其合成方法
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107141252A (zh) * 2017-06-26 2017-09-08 常州大学 一种类水滑石材料催化含氮杂环化合物氧化脱氢的方法
CN107376970A (zh) * 2017-07-25 2017-11-24 中国石油大学(北京) 单原子铁掺氮多孔碳催化剂及其制备方法与应用
CN107376970B (zh) * 2017-07-25 2020-04-24 中国石油大学(北京) 单原子铁掺氮多孔碳催化剂及其制备方法与应用
CN107353245A (zh) * 2017-08-24 2017-11-17 福州大学 一种喹啉类化合物的合成方法
CN107353245B (zh) * 2017-08-24 2019-06-04 福州大学 一种喹啉类化合物的合成方法
CN109529907A (zh) * 2018-12-30 2019-03-29 中南民族大学 一种氮掺杂碳材料负载钴催化剂及其制备方法和在n-杂环化合物催化氧化中的应用
CN109529907B (zh) * 2018-12-30 2021-10-15 中南民族大学 一种氮掺杂碳材料负载钴催化剂及其制备方法和在n-杂环化合物催化氧化中的应用
CN113024458A (zh) * 2019-12-09 2021-06-25 中国科学院大连化学物理研究所 一种生物质基碳材料实现含氮杂环氧化脱氢的方法
CN113024458B (zh) * 2019-12-09 2022-06-07 中国科学院大连化学物理研究所 一种生物质基碳材料实现含氮杂环氧化脱氢的方法
CN113929610A (zh) * 2021-11-17 2022-01-14 甘肃警察职业学院 一种基于离子液体多孔碳材料催化氮杂环需氧脱氢的方法
CN116272943A (zh) * 2023-03-24 2023-06-23 遵义医科大学 一种碳基非金属催化剂及其制备方法和应用
CN116272943B (zh) * 2023-03-24 2024-06-11 遵义医科大学 一种碳基非金属催化剂及其制备方法和应用

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