CN109970659B - 一种采用负载型镍催化剂制备苯并咪唑和喹唑啉类化合物的方法 - Google Patents
一种采用负载型镍催化剂制备苯并咪唑和喹唑啉类化合物的方法 Download PDFInfo
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- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 title claims abstract description 15
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
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Abstract
本发明公开了一种利用氮掺杂分级多孔生物质基碳材料负载催化剂氧化偶联脱氢合成苯并咪唑和喹唑啉类化合物的方法。该方法在密闭条件下向反应管内加入邻苯二胺类化合物、醇、负载型催化剂、作为溶剂的甲苯和叔丁醇钾,于50~150℃下进行反应,反应4~24小时后,冷却至室温,过滤反应液,即得苯并咪唑类化合物或喹唑啉类化合物。该方法采用“一锅法”制备,无需对中间体进行分离纯化,可降低能耗,提高效率。
Description
技术领域
本发明属于能源化工,具体涉及一种利用氮掺杂分级多孔生物质基碳材料负载催化剂氧化偶联脱氢合成苯并咪唑和喹唑啉类化合物的方法。该方法采用“一锅法”制备,无需对中间体进行分离纯化,可降低能耗,提高效率。
背景技术
含氮杂环化合物在医药和农药方面都具有广泛的应用前景,特别是广泛存在于自然界中的苯并咪唑类和喹唑啉类化合物。在过去的几十年中,含有苯并咪唑和喹唑啉的杂环化合物的合成和生物学评价在药物发现和开发领域中获得了极大的重视。
苯并咪唑也被称为环加氧酶抑制剂,选择性醛糖还原酶抑制剂和AMP-蛋白激酶活化剂,具有多种生物活性,是药物化学中有前途的支架。苯并咪唑的两个芳环可通过氢键或疏水相互作用与酶或受体结合,使其具有广泛的生物活性,如抗癌,抗炎,镇痛,抗菌,抗氧化,抗结核,抗真菌,抗糖尿病和抗惊厥活性。例如
传统合成苯并咪唑的方法主要包括:1)2-氨基苯胺与各种醛、胺或者酸类的缩合;2)以2-氨基苯胺与醇作为原料;3)以邻硝基苯胺和醇作为起始原料三种方法。然而这些有机合成方法屮均存在反应底物选择范围狭小和较高的反应温度,反应时间长和反应压力高等问题。
喹唑啉是多种生物碱和药物的基本骨架结构,由于其结构简单、易于改造,是新型农药创制和医药合成的重要中间体。其通常存在于各种生物碱和功能分子中,是多种药物分子的核心结构骨架,如:哌唑嗪、拉帕替尼和埃克替尼等。其具有多种生物学和药理学活性,例如抗癌,抗疟疾,抗炎,抗菌,抗惊厥,抗结核和抗高血压性质。例如
传统合成喹唑啉的方法,其主要包括邻氨基苄胺与醛等价物如醛和醇的氧化缩合;邻氨基或邻卤代芳基羰基与胺基或氨及碳源(如醛和DMF/DMA)的反应;脒与邻卤代苄胺或邻卤代苄基卤化物的偶联;芳基脒与醛或官能化的炔烃当量的缩合;2-氨基芳基醇和腈通过碱基催化原位生成2-氨基芳基醛/酮和酰胺,一步合成喹唑啉。然而这些有机合成方法中仍然存在苛刻的反应条件,使用不易获得的底物,贵金属催化剂,配体,对环境不利的溶剂,或大量的碱或氧化剂,可导致产品中的金属污染,废物的产生和低原子经济性等缺点。这些在很大程度上限制了喹唑啉衍生物在药物合成中的应用。
在各种类型的氧化偶联脱氢反应中,使用醇作为底物的反应引起了特别的兴趣。这是由于(i)易于获得且通常醇的低成本,和(ii)这些方法的环境友好和原子经济性质。通过形成C-O,C-N,C-S,C-C和C=C键,这些反应可以作为偶联醇与各种亲核试剂的简单方法。首先通过催化剂的脱氢反应,将相对惰性的底物醇活化成可进行各种转化的重要亲电中间体羰基化合物,后可与氨基或羟基形成亚胺或烯烃(C=X)。醇与合适的偶联剂的氧化偶联脱氢只有H2O作为化学废物产生,已成为一种具有吸引力的原子经济和环境友好的合成杂环化合物的方法。然而,以往关于过渡金属催化合成苯并咪唑和喹唑啉类化合物的报道大都使用稀有的贵金属作催化剂,如Ir、Pt、Pd等,限制了其在实际生产中广泛的应用。从环境友好、原子高效的角度考虑,开发廉价易得的非贵金属多相催化以绿色温和的方式促进的醇与二氨基芳香化合物氧化偶联脱氢构建苯并咪唑和喹唑啉类化合物更具有经济价值和实际意义。
发明内容
针对上述现有技术中的问题,根据本发明的目的在于提供一种利用氮掺杂分级多孔生物质基碳材料负载催化剂氧化偶联脱氢合成苯并咪唑和喹唑啉类化合物的方法。
为实现上述目的,本发明采用技术方案如下反应式表示:
其中,取代基R1选自氢、氰基、C1-C3烷氧基、C1-C3烷基、卤素和C1-C3烷氧基羰基中;m为选自0、1、2或3的整数。
n为选自0或1的整数。
取代基R2选自苯基、取代的苯基、联苯基、C1-C10烷基、苯基取代的C1-C3烷基、噻吩基、三氟甲基中,其中所述取代的苯基中苯环上含有1至3个选自氰基、C1-C3烷氧基、C1-C3烷基、卤素和C1-C3烷氧基羰基中的取代基。
所述卤素选自氟、氯或溴。
根据本发明的合成方法包括以下步骤:
在密闭条件下向反应釜内加入式1表示的邻苯二胺类化合物、醇负载型催化剂、作为溶剂的甲苯和叔丁醇钾,于50~150℃下进行反应,反应4~24小时后,冷却至室温,过滤反应液,TLC检测后再由硅胶柱层析,即得式2所示苯并咪唑类化合物或式3所示喹唑啉类化合物,之后采用氢核磁和碳核磁检测确认目标产物。
其中,所述负载型催化剂由1wt%~25wt%的金属粒子和75wt%~99wt%的生物基氮掺杂多孔碳材料载体构成,金属粒子为镍,所述负载型催化剂的比表面积50~600m2/g。
优选地,所述负载型催化剂由0.5wt%~10wt%的镍粒子和90wt%~99.5wt%的生物基氮掺杂多孔碳材料载体构成,负载型催化剂的比表面积优选为50~500m2/g。
当目标产物为式2所示苯并咪唑类化合物时,所述负载型催化剂用量为1,2-苯二胺重量的80%~200%,醇类化合物的量为1,2-苯二胺物质的量的1~3倍,叔丁醇钾的量为1,2-苯二胺物质的量的0.1~0.8倍。
进一步优选地,当目标产物为式2所示苯并咪唑类化合物时,所述负载型催化剂用量为1,2-苯二胺重量的100%~150%,醇类化合物的量为1,2-苯二胺物质的量的1~2倍,叔丁醇钾的量为1,2-苯二胺物质的量的0.2~0.4倍。
进一步优选地,当目标产物为式3所示喹唑啉类化合物时,所述负载型催化剂用量为2-氨基苄胺重量的100%~150%,醇类化合物的量为2-氨基苄胺物质的量的1~2倍,叔丁醇钾的量为2-氨基苄胺物质的量的0.2~0.4倍。
优选地,反应温度为100~120℃,反应时间为4~20小时。
优选地,所述负载型催化剂按照如下制备方法制备得到:
1)以富含蛋白的生物质为原料,将其干燥研磨成粉末后,加入一定量的水,搅拌均匀后移到水热反应釜中,于180℃加热5.5小时,反应完成后经过滤、洗涤、干燥等一系列后处理步骤后得到棕色固体,然后将其研磨成粉末,取1g所述干燥固体粉末分散于30mL溶有0.099g Ni(CH3COO)2.4H2O的水溶液中,后加入120微升植酸搅拌均匀干燥,待用;
2)将所得固体在惰性气体的氛围中进行煅烧;煅烧温度为300~1500℃,保温时间为0.5~100小时,煅烧后降至室温,即得负载型催化剂。
其中,所述负载型催化剂由1wt%~25wt%的金属粒子和75wt%~99wt%的生物基氮掺杂多孔碳材料载体构成,金属粒子为镍,所述负载型催化剂的比表面积50~600m2/g。
优选地,所述负载型催化剂由0.5wt%~10wt%的镍粒子和90wt%~99.5wt%的生物基氮掺杂多孔碳材料载体构成,负载型催化剂的比表面积优选为50~500m2/g。
有益效果
本发明采用廉价的金属镍纳米催化剂通过“一锅法”串联反应这一绿色合成化学策略,以廉价易得的二胺类芳香化合物为原料实现和苄醇类化合物的氧化偶联脱氢反应从而制备得到苯并咪唑和喹唑啉类化合物。较以往的贵金属催化体系,该反应体系操作简便、条件温和、成本低廉,有利于大规模生产和工业化应用。
附图说明
图1和图2为本发明实施例1、2、3和4制备的负载型催化剂BET测试结果。
图3为本发明实施例1、2、3和4制备的负载型催化剂的XRD测试结果图。
图4为本发明实施例1催化剂循环效果柱状图。
具体实施方式
以下,将详细地描述本发明。在进行描述之前,应当理解的是,在本说明书和所附的权利要求书中使用的术语不应解释为限制于一般含义和字典含义,而应当在允许发明人适当定义术语以进行最佳解释的原则的基础上,根据与本发明的技术方面相应的含义和概念进行解释。因此,这里提出的描述仅仅是出于举例说明目的优选实例,并非意图限制本发明的范围,从而应当理解的是,在不偏离本发明的精神和范围的情况下,可以由其获得其他等价方式或改进方式。
本发明以磷氮掺杂多孔碳作为载体负载金属镍的催化剂,该催化剂由1wt%~25wt%的金属粒子和75wt%~99wt%的生物质基氮掺杂多孔碳材料载体构成,可用于二胺芳香化合物和卞醇类化合物氧化偶联脱氢反应制备苯并咪唑和喹唑啉类化合物,反应条件温和,只以密封反应管中的空气中的氧气成分为氧化剂,不需要使用常规氧化剂。所述催化剂的所有原料为可再生资源,分布广泛,绿色环保,简单易得,资源丰富,价格低廉,且催化剂可循环使用不失活,对空气、水和热都很稳定。根据本发明的负载型金属催化剂,二胺芳香化合物和卞醇类化合物氧化偶联脱氢反应制备苯并咪唑类化合物转化率大于99%,产物可达90%~60%,制备喹唑啉类化合物转化率大于99%,产物可达90%~60%。
以下实施例仅是作为本发明的实施方案的例子列举,并不对本发明构成任何限制,本领域技术人员可以理解在不偏离本发明的实质和构思的范围内的修改均落入本发明的保护范围。除非特别说明,以下实施例中使用的试剂和仪器均为市售可得产品。
表征所用仪器:
1)透射电子显微镜:型号为H-7650,生产厂家为Hitachi日立公司
2)元素分析仪:型号为Vario-EL-cube,生产厂家为德Elementary公司
3)物理吸附仪:型号为ASAP2020,生产厂家为美国micrometritics公司
4)核磁共振波谱仪:型号为DRX-400生产厂家为美国德国Bruker公司
实施例1:氮掺杂多孔碳材料负载型Ni催化剂的制备
将1kg清洗干净的竹笋切成碎片,在烘箱中70℃加热至干燥,将干燥后所得固体研成粉末,待用;取4g粉末加入40mL水中,搅拌混合均匀后移到水热反应釜中,于180℃反应5.5小时,反应后经过滤、过滤后产物经水洗涤,干燥得到褐色固体,将所得固体真空干燥24小时、研磨至颗粒均匀得水热碳。之后将上述得到褐色固体水热碳0.5g分散于溶有0.0498gNi(CH3COO)2.4H2O和60μL植酸的15mL水中,60℃下搅拌2h,将该反应液置于100摄氏度下干燥12h,之后将得到的干燥固体放于管式炉中在氮气气体氛围中煅烧,并在800℃下保温2小时,待管式炉降到室温后将样品拿出,即得到氮和磷掺杂多孔负载镍催化剂,表示为Ni/CNP-800,其比表面积为51.27m2/g,由BET分析可见该催化剂具有大孔、介孔、微孔等分级结构的孔组成。(参见图1和图2)。
实施例2
除了在制备过程中,没有加入植酸以外,按照实施例1相同的方式制备不掺杂磷多孔碳材料负载型Ni催化剂,表示为Ni/CN-800。
实施例3
除了在700℃下保温2小时以外,按照实施例1相同的方式制备氮和磷掺杂多孔碳材料负载型Ni催化剂,表示为Ni/CNP-700。
实施例4
除了在900℃下保温2小时以外,按照实施例1相同的方式制备氮和磷掺杂多孔碳材料负载型Ni催化剂,表示为Ni/CNP-900。
将上述制备获得氮或磷掺杂碳材料负载镍催化剂进行X射线衍射分析,所得的X射线衍射图谱如图3所示,从图3中可以看出,不掺杂磷的Ni/CN-800催化剂形成的是镍单质峰,而800度和900度温度下煅烧的掺杂磷的Ni催化剂形成了令人欣喜的Ni2P纳米颗粒峰,且900℃下煅烧所得催化剂Ni2P峰相对较800度煅烧的强。且Ni2P作为一种过渡金属磷化物(TMP),由于其低成本和在碱性介质下催化HER和OER反应具有有利的催化活性,可作为取代贵金属基电催化剂的候选物。而700度煅烧的镍催化剂因为煅烧温度不足,没有任何金属晶粒的形成。
实施例5:
利用实施例1中制备的氮磷掺杂碳材料负载镍催化剂催化1,2-苯二胺和苄醇氧化偶联脱氢制备苯并咪唑类化合物的方法。其步骤是:0.2mmol 1,2-苯二胺、0.2mmol苄醇、30mg所述负载型催化剂、2mL甲苯,6.72mg(0.06mmol)叔丁醇钾,密闭后在120℃下进行反应,反应12小时后,冷却至室温,过滤反应液,硅胶柱层析即得2-苯基-1氢-苯并咪唑化合物;
2-苯基-1氢-苯并咪唑:1H NMR(400MHz,DMSO):δ8.19(s,2H),7.59(m,5H),7.22(s,2H);13C NMR(101MHz,DMSO):δ151.7,139.8,130.5,130.4,129.4,126.9,122.6,115.7。
与实施例5操作和步骤相同,改变1,2-苯二胺和不同取代的苄醇类化合物(即底物)的种类,得到的苯并咪唑类化合物(产物)、转化率均>99%、产率60~90%不等,具体如表1所示:
表1
实施例19:
利用实施例1中制备的氮磷掺杂碳材料负载镍催化剂催化2-氨基苄胺和苄醇化合物氧化偶联脱氢制备喹唑啉化合物的方法。其步骤是:在反应管中加入0.2mmol 2-氨基苄胺、0.2mmol苄醇化合物、30mg所述负载型催化剂、2mL甲苯,6.72mg(0.06mmol)叔丁醇钾,密闭后在120℃下进行反应,反应12小时后,冷却至室温,过滤反应液,硅胶柱层析即得2-苯基-喹唑啉化合物。
2-苯基-喹唑啉:1H NMR(400MHz,CDCl3):δ(ppm)=9.47(s,1H),8.67-8.65(m,2H),8.10(d,J=8.8Hz,1H),7.92-7.88(m,2H),7.61-7.53(m,4H);13C NMR(100MHz,CDCl3):δ(ppm)=160.9,160.4,150.6,138.0,134.0,130.5,128.5(2C),128.5,127.1,127.0,123.5.
与实施例19操作和步骤相同,改变2-氨基苄胺和不同取代的苄醇类化合物(即底物)的种类,得到的喹唑啉类化合物(产物)、转化率均>99%、产率60~90%不等,具体如表2所示:
表2
实施例31:二胺芳香化合物和不同取代苄醇类化合物氧化偶联脱氢制备苯并咪唑和喹唑啉类化合物催化剂循环:
以2-氨基苄胺和苄醇的氧化偶联脱氢作为模板反应进行催化剂循环实验,其步骤是:
在反应管中加入0.2mmol 2-氨基苄胺、0.2mmol苄醇、30mg所述负载型催化剂、2mL甲苯,6.72mg(0.06mmol)叔丁醇钾,密闭后在120℃下进行反应,反应12小时后,冷却至室温,过滤反应液,对反应液进行气相色谱分析。将反应液离心(10000rpm,15min),将上清液移除,随后加入5mL乙醇、离心移除上清液,以上操作重复3次,所得固体在真空干燥箱内40℃下干燥12h,以备下一轮催化剂循环使用,由循环实验可见催化剂在重复使用5次后仍然能保持高活性和稳定性(循环效果如图4所示)。
Claims (7)
1.一种利用氮掺杂分级多孔生物质基碳材料负载催化剂氧化偶联脱氢合成苯并咪唑和喹唑啉类化合物的方法,所述方法由如下反应式表示:
其中,取代基R1选自氢、氰基、C1-C3烷氧基、C1-C3烷基、卤素和C1-C3烷氧基羰基中;m为选自0、1、2或3的整数;
n为选自0或1的整数;
取代基R2选自苯基、取代的苯基、联苯基、C1-C10烷基、苯基取代的C1-C3烷基、噻吩基、三氟甲基中,其中所述取代的苯基中苯环上含有1至3个选自氰基、C1-C3烷氧基、C1-C3烷基、卤素和C1-C3烷氧基羰基中的取代基;
所述卤素选自氟、氯或溴;
所述合成方法包括以下步骤:
在密闭条件下向反应釜内加入式1表示的邻苯二胺类化合物、醇负载型催化剂、作为溶剂的甲苯和叔丁醇钾,于50~150℃下进行反应,反应4~24小时后,冷却至室温,过滤反应液,TLC检测后再由硅胶柱层析,即得式2所示苯并咪唑类化合物或式3所示喹唑啉类化合物,之后采用氢核磁和碳核磁检测确认目标产物;
所述负载型催化剂按照如下制备方法制备得到:将1kg清洗干净的竹笋切成碎片,在烘箱中70℃加热至干燥,将干燥后所得固体研成粉末,待用;取4g粉末加入40mL水中,搅拌混合均匀后移到水热反应釜中,于180℃反应5.5小时,反应后经过滤、过滤后产物经水洗涤,干燥得到褐色固体,将所得固体真空干燥24小时、研磨至颗粒均匀得水热碳,之后将上述得到褐色固体水热碳0.5g分散于溶有0.0498g Ni(CH3COO)2.4H2O和60μL植酸的15mL水中,60℃下搅拌2h,将该反应液置于100摄氏度下干燥12h,之后将得到的干燥固体放于管式炉中在氮气气体氛围中煅烧,并在800℃下保温2小时,待管式炉降到室温后将样品拿出,即得到所述负载镍催化剂。
6.根据权利要求1所述的合成方法,其特征在于,反应温度为100~120℃,反应时间为4~20小时。
7.根据权利要求1所述的合成方法,其特征在于,所述负载型催化剂的比表面积为51.27m2/g。
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