CN112375041B - 一种2位取代苯并咪唑类化合物的制备方法 - Google Patents
一种2位取代苯并咪唑类化合物的制备方法 Download PDFInfo
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- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- 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
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
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Abstract
本发明公开了一种2位取代苯并咪唑类化合物的制备方法,属于苯并咪唑类化合物的合成领域。本发明以邻硝基苯胺类化合物和芳香醛、邻二硝基苯和芳香醛为原料,以氮掺杂碳材料包裹Co粒子为催化剂,在有机溶剂中合成2位取代苯并咪唑类化合物。该方法可在室温下制备2位取代苯并咪唑类化合物,反应条件温和,产率高达95%,选择性高达99%,且经济环保,底物适用性广。而且所用催化剂容易制备、成本低廉,重复使用性好,可利用磁性进行分离,回收便捷,因此具有较强的工业应用前景。
Description
技术领域
本发明涉及苯并咪唑类化合物的合成领域,具体涉及一种2位取代苯并咪唑类化合物的制备方法。
背景技术
苯并咪唑类化合物是一种含有2个氮原子的苯并杂环化合物,具有更稳定的电子离域体系。这类化合物是多种药物的结构单元和中间体,具有抗真菌、抗肿瘤、消炎、抗寄生虫的功效,还可以用于表面活性处理剂、环氧树脂新型固化剂、化学发光等方面。传统合成方法有两种:一种是邻苯二胺和羧酸衍生物缩合法(见下合成路线A),邻苯二胺与有机酸在加热条件下脱水、环化制得,该方法需要较高的反应温度且需要用到大量的酸,对仪器设备要求较高。另一种是邻苯二胺与醛类化合物反应合成(见下合成路线B),该反应副反应比较多,分离比较困难,产率较低。
利用邻硝基苯胺合成2位取代的苯并咪唑的方法已有报道。在催化剂的作用下实现苯甲醇与邻硝基苯胺之间的氧化还原合成2位取代苯并咪唑(见下合成路线C)(文献:LiGang,Wang,Jin,Yuan,Baokun.Tetrahedron Letters,2013,54,6934-6936;Feng Feng,Ye,Jia Cheng,Zheng.RSC Advances,2016,76,72750-72755)。在还原性化合物的作用下,邻硝基苯胺与芳香醛合成2取代苯并咪唑。(见下合成路线D)(文献:Fokas Demosthenes,YangDonglai,Li Jingzhou.Synthesis,2005,01,47-56;毛郑州,汪朝阳,宋秀美.有机化学,2009,09,985-988)。以贵金属为催化剂在氢气的氛围中催化邻硝基苯胺与芳香醛合成2位取代苯并咪唑。(文献:Nicholas A.Weires,Jared Boster,Jakob Magolan.European JOrg Chem.2012,33,6508-6512;Malhari D.Bhor and Bhalchandra M.Bhanage.SyntheticCommunications.2010,12,1743-1749)。尽管2位取代苯并咪唑的合成早有研究,但是大多数催化体系都存在着反应温度高(>120℃),反应条件苛刻(需要加入强还原剂),需用到贵金属,反应时间长,催化剂易中毒及难以回收利用等缺点,因此大大限制了其工业应用。
发明内容
为了克服以上的不足,本发明的目的在于提供一种2位取代苯并咪唑类化合物的制备方法,该方法以氮掺杂碳材料包裹Co粒子(Co/NC)作为催化剂,合成了2位取代苯并咪唑类化合物,该方法条件温和、绿色、经济、实用性强。
本发明的目的通过下述技术方案实现。
一种2位取代苯并咪唑类化合物的制备方法,包括以下步骤:
将芳香醛、硝基苯类化合物与溶剂混合,在催化剂和氢气的作用下反应,即合成2位取代苯并咪唑类化合物;所述硝基苯类化合物为邻硝基苯胺类化合物或邻二硝基苯;所述催化剂为氮掺杂碳材料包裹Co粒子复合材料。
优选的,该方法的反应路线如下:
所述R1为H、甲基、甲氧基、卤素或叔丁基;所述R2为2-甲基苯基、3-甲基苯基、4-甲基苯基、4-氟苯基、4-氯苯基、4-溴苯基、4-甲氧基苯基、α-萘基、2-呋喃基、2-噻吩基或2-吡啶基。
优选的,所述催化剂由以下步骤制备而得:
将P123(聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物)、四水合乙酸钴、三聚氰胺分散在水中,搅拌均匀后进行回流反应,再将所得前驱体在氮气的氛围中700℃-900℃煅烧,得氮掺杂碳材料包裹Co粒子复合材料。
优选的,所述煅烧的温度为900℃,所得催化剂标记为Co/NC900。
优选的,所述催化剂由以下步骤制备而得:
1)将P123 1.5g、四水合乙酸钴1g、三聚氰胺2.25g分散在80ml去离子水中,室温搅拌3h后转移至80℃油浴装置中回流反应0.5h,最后利用旋转蒸发仪除去溶剂。
2)将步骤1)中制备的前驱体在氮气的氛围中煅烧,以2℃·min-1的升温速率升温至180℃、240℃和最高温度,(最高温度为700℃、800℃、900℃)分别在上述温度下维持2h、2h和1h。
3)将步骤2)中煅烧的材料放入浓度为1mol·L-1的盐酸中80℃洗涤12h,并用去离子水清洗后,放入80℃烘箱干燥12h。
优选的,所述反应的温度为室温至100℃。
优选的,所述氢气的压力为1-4MPa。
优选的,所述反应的时间为12-20h。
优选的,所述催化剂与硝基苯类化合物的质量比为1:2-2:3。
优选的,所述溶剂为甲醇或乙酸乙酯。
优选的,所述的催化剂为Co/NC900,反应的温度为室温,氢气压力为1MPa,反应时间为16h,催化剂与硝基苯类化合物的质量比为1:2,溶剂为乙酸乙酯,反应物芳香醛与硝基苯类化合物的摩尔比为2:1,2-苯基苯并咪唑产率为95%。
与现有技术相比,本发明具有以下优点:
1.由本发明方法合成的衍生物中,2-呋喃基苯并咪唑为市场上常用的农药,商品名为麦穗宁,本发明方法合成条件温和,所得的产率较高(95%)。因此本发明具有较高的经济效益。
2.工业上的2-苯基苯并咪唑通常由邻苯二胺与苯甲醛制备所得,其副反应多、产率不高是限制该方法应用的主要因素。而邻苯二胺通常由邻硝基苯胺还原制得,本发明直接由邻硝基苯胺与苯甲醛在室温下一步合成2-苯基苯并咪唑,省略了工业上邻硝基苯胺还原为邻苯二胺这一步骤,最终本反应产率达到95%,转化率高达99%。
3.本发明催化体系条件温和,绿色环保,产率高。底物适用范围广,合成了19个2位取代苯并咪唑衍生物。
4.本发明所用催化剂的制备方法只需简单的混合、搅拌、灼烧和清洗等步骤,使用过渡金属钴盐、三聚氰胺和P123为原料,成本较低。催化反应完成后,利用催化剂本身具有的磁性实现分离,操作便捷。由于碳材料包裹着Co粒子,使得该催化剂结构稳定,Co粒子不易流失,因此催化剂重复使用性好。
附图说明
图1为本发明所用催化剂的磁性分离示意图。
图2为本发明所用催化剂的XRD图。
图3为本发明所用催化剂Co/NC900的扫描电镜图与透射电镜图;其中,a)为Co/NC900扫描电镜图,b-d)为Co/NC90透射电镜图。
图4为本发明所用催化剂的回收利用效果图。
具体实施方式
下面结合实施例与附图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。
实施例1催化剂煅烧温度对反应的影响
本发明采用的催化剂按照W.Yang,L.Chen,X.Liu,J.Jia,S.Guo,Nanoscale 2017,9,1738-1744中的方法制备,具体步骤如下:
将P123 1.5g、四水合乙酸钴1.0g、三聚氰胺2.25g均匀地分散在80ml去离子水中,室温搅拌3h后转移至80℃油浴装置中加热回流0.5h,反应后利用旋转蒸发仪除去水。而后将粉末置于刚玉管中,在氮气的氛围中煅烧,以2℃·min-1的升温速率升温至180℃、240℃和最高温度(700℃、800℃和900℃),分别维持2h、2h和1h。将得到的黑色粉末放入浓度为1mol·L-1的盐酸中恒温(80℃)酸洗12h后用去离子水和乙醇洗涤至中性,放入80℃烘箱干燥12h。不同最高煅烧温度制得的催化剂分别记为Co/NC700、Co/NC800和Co/NC900。
在25mL不锈钢高压釜中,以邻硝基苯胺(0.2mmol)、苯甲醛(0.4mmol)为反应底物、催化剂分别为Co/NC700、Co/NC800、Co/NC900(10mg),溶剂为乙酸乙酯(4mL),高压反应釜内的空气用H2置换三次(高压反应釜经H2置换三次,排出空气,减少其对反应的干扰),将H2压力升至1.0MPa,保证高压釜不漏气后,将其放入油浴锅中室温搅拌反应20h。反应结束后,将反应液过滤于容量瓶中,以邻硝基苯胺为计算标准,通过GC计算产率(如表1示),可见同等条件下催化剂煅烧温度越高,催化活性越强。
表1.催化剂煅烧温度对合成4a的影响
反应条件:催化剂(10mg),1a(0.2mmol),2a(0.4mmol),乙酸乙酯(4mL),H2(1.0MPa),室温,时间(20h)。
由表1可知,催化剂的最高煅烧温度优选为900℃。
实施例2温度对催化反应的影响
在25mL不锈钢高压釜中,加入邻硝基苯胺(0.2mmol)、苯甲醛(0.4mmol)、催化剂Co/NC900(20mg)和乙酸乙酯(4mL),H2压力升至4.0MPa,将其放入目标温度为室温至100℃油浴锅中搅拌反应20小时。以邻硝基苯胺为计算标准,通过GC计算产率(如表2所示)。
表2.反应温度对合成4a的影响
反应条件:催化剂(20mg),1a(0.4mmol),2a(0.2mmol),乙酸乙酯(4mL),H2(4.0MPa),温度(室温-100℃),时间(20h)。
由表2可知,反应温度优选为室温。
实施例3氢气压力对催化反应的影响
在25mL不锈钢高压釜中,加入邻硝基苯胺(0.2mmol)、苯甲醛(0.4mmol)、催化剂Co/NC900(20mg)和乙酸乙酯(4mL),将H2压力升到1.0-4.0MPa,将其放入油浴锅中室温搅拌反应20h。反应结束后,以邻硝基苯胺为计算标准,通过GC计算产率(如表3所示)。
表3.氢气压力对合成4a的影响
反应条件:催化剂(20mg),1a(0.4mmol),2a(0.2mmol),乙酸乙酯(4mL),H2(1.0-4.0MPa),室温,时间(20h)。
由表3可知,氢气压力优选为1MPa。
实施例4反应时间对催化反应的影响
在25mL不锈钢高压釜中,加入邻硝基苯胺(0.2mmol)、苯甲醛(0.4mmol)、催化剂Co/NC900(20mg)和乙酸乙酯(4mL),将H2压力升至1.0MPa,将其放入油浴锅中室温搅拌反应4-20h。反应结束后,以邻硝基苯胺为计算标准,通过GC计算产率(如表4所示)。
表4.反应时间对合成4a的影响
反应条件:催化剂(20mg),1a(0.4mmol),2a(0.2mmol),乙酸乙酯(4mL),H2(1.0MPa),室温,时间(4-20h)。
由表4可知,反应时间优选为16h。
实施例5催化剂用量对反应的影响
在25mL不锈钢高压釜中,加入邻硝基苯胺(0.2mmol)、苯甲醛(0.4mmol)、催化剂Co/NC900(5-20mg)和乙酸乙酯(4mL),高压反应釜里的空气用H2置换三次后将H2压力升至1.0MPa,保证高压釜不漏气后,将其放入油浴锅中室温搅拌反应16h。反应结束后,以邻硝基苯胺为计算标准,通过GC计算产率(如表5示)。
表5.催化剂用量对合成4a的影响
反应条件:催化剂(5-20mg),1a(0.2mmol),2a(0.4mmol),乙酸乙酯(4mL),H2(1.0MPa),室温,时间(16h)。
由表5可知,催化剂的用量优选为15mg。
实施例6溶剂对反应的影响
在25mL不锈钢高压釜中,加入邻硝基苯胺(0.2mmol)、苯甲醛(0.4mmol)、催化剂Co/NC900(15mg),溶剂分别为甲醇、乙醇、乙腈、四氢呋喃、乙酸乙酯(4mL),将H2压力升至1.0MPa,将其放入油浴锅中室温搅拌反应16h。反应结束后,以邻硝基苯胺为计算标准,通过GC计算产率(如表6示)。优选溶剂为乙酸乙酯。
表6.溶剂对合成4a的影响
反应条件:催化剂(15mg),1a(0.2mmol),2a(0.4mmol),溶剂(4mL),H2(1.0MPa),室温,时间(16h)。
由表6可知,溶剂优选为乙酸乙酯。
实施例7芳香醛上取代基对反应的影响
为研究该反应的普适性,在不锈钢高压釜中,加入邻硝基苯胺(0.2mmol)、芳香醛(0.4mmol)、催化剂Co/NC900(20mg),乙酸乙酯(4mL),将H2压力升至1.0MPa,将其放入目标温度油浴锅中搅拌反应20h。反应结束后,以邻硝基苯胺为计算标准,通过GC计算产率(如表7所示)。该方法对于2位取代苯并咪唑类化合物的合成具有普适性,芳香环上含有致活的给电子基、致钝的吸电子基或是含杂原子的芳香醛,均有较高的产率。
表7.邻硝基苯胺与芳香醛合成2位取代苯并咪唑
反应条件:催化剂(20mg),1(0.4mmol),2a(0.2mmol),乙酸乙酯(4mL),H2(1.0MPa),60℃,时间(20h)a反应温度为100℃,产率由液相色谱(HPLC)测得。b反应温度为130℃,产率由液相色谱(HPLC)测得。
实施例8邻硝基苯胺上取代基对反应的影响
此外,为研究不同取代的邻硝基苯胺对该反应的影响,在不锈钢高压釜中,加入邻硝基苯胺衍生物(0.2mmol)、苯甲醛(0.4mmol)、催化剂Co/NC900(20mg),乙酸乙酯(4mL),将H2压力升至1.0MPa,保证高压釜不漏气后,将其放入目标温度油浴锅中搅拌反应20h。反应结束后,以邻硝基苯胺衍生物为计算标准,通过GC计算产率(如表8所示),该方法对于合成2位取代苯并咪唑衍生物的合成具有普适性,即使邻硝基苯胺的苯环上含有致活的给电子基或是致钝的吸电子基,也能高效合成产物(产率94%-99%)。
表8.邻硝基苯胺衍生物与苯甲醛合成2位取代苯并咪唑
反应条件:催化剂(20mg),1a(0.4mmol),2(0.2mmol),乙酸乙酯(4mL),H2(1.0MPa),60℃,时间(20h)。
实施例9邻二硝基苯与芳香醛合成2位取代苯并咪唑
在不锈钢高压釜中,加入邻二硝基苯(0.2mmol)、芳香醛(0.4mmol)、催化剂Co/NC900(20mg),乙酸乙酯(4mL),高压反应釜里的空气用H2置换三次后将H2压力升至1.0MPa,将其放入目标温度油浴锅中搅拌反应20h。反应结束后,以邻二硝基苯为计算标准,通过GC计算产率(如表9所示)结果总结,结果显示邻二硝基苯同样适用于本方法合成2位取代苯并咪唑衍生物,且具有较高的产率。
表9.邻二硝基苯与芳香醛合成2位取代苯并咪唑
反应条件:催化剂(20mg),2(0.4mmol),3(0.2mmol),乙酸乙酯(4mL),H2(1.0MPa),70℃,时间(20h)。a反应温度为100℃,产率由液相色谱(HPLC)测得。b反应温度为130℃,产率由液相色谱(HPLC)测得。
图1为本发明所用催化剂的磁性分离过程,催化剂Co/NC反应完毕后,利用其自身的磁性可以实现快速分离,实现重复使用。
图2为本发明所用催化剂Co/NC的XRD图,所制备的材料含有单质(111)、Co(200)、(220)晶面和C(002)晶面的衍射峰,结合图3中的透射电镜图说明成功制备出氮掺杂碳材料包裹钴粒子复合材料。
图3为Co/NC900的透射电镜图,金属钴粒子被包裹在竹节状的碳材料中。
图4为本发明所用催化剂回收利用图,反应条件:催化剂(10mg),1a(0.4mmol),2a(0.2mmol),乙酸乙酯(4mL),PH2(1.0MPa),室温,时间(20h),可以看出催化剂循环使用6次后仍能稳定存在。
Claims (8)
1.一种2位取代苯并咪唑类化合物的制备方法,其特征在于,包括以下步骤:
将芳香醛、硝基苯类化合物与溶剂混合,在催化剂和氢气的作用下反应,即合成2位取代苯并咪唑类化合物;所述硝基苯类化合物为邻硝基苯胺类化合物或邻二硝基苯;所述催化剂为氮掺杂碳材料包裹Co粒子复合材料,标记为Co/NC;
所述Co/NC由以下步骤制备而得:
将P123、四水合乙酸钴、三聚氰胺分散在水中,搅拌均匀后进行回流反应,再将所得前驱体在氮气的氛围中700℃-900℃煅烧,酸洗,得氮掺杂碳材料包裹Co粒子复合材料;
所述反应的温度为室温至100℃。
3.根据权利要求1所述的一种2位取代苯并咪唑类化合物的制备方法,其特征在于,所述煅烧的温度为900°C,所得催化剂标记为Co/NC900。
4.根据权利要求1-3任一项所述的一种2位取代苯并咪唑类化合物的制备方法,其特征在于,所述氢气的压力为1-4 MPa。
5.根据权利要求1-3任一项所述的一种2位取代苯并咪唑类化合物的制备方法,其特征在于,所述反应的时间为12-20 h。
6.根据权利要求1-3任一项所述的一种2位取代苯并咪唑类化合物的制备方法,其特征在于,所述催化剂与硝基苯类化合物的质量比为1:2-2:3。
7.根据权利要求1-3任一项所述的一种2位取代苯并咪唑类化合物的制备方法,其特征在于,所述溶剂为甲醇或乙酸乙酯。
8.根据权利要求1-3任一项所述的一种2位取代苯并咪唑类化合物的制备方法,其特征在于,所述的催化剂为Co/NC900,反应的温度为室温,氢气压力为1MPa,反应时间为16 h,催化剂与硝基苯类化合物的质量比为1:2,溶剂为乙酸乙酯,反应物芳香醛与硝基苯类化合物的摩尔比为2:1。
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