CN113801037A - 硝基芳烃和烷基或苯基硼酸一步法制备c-n偶联产物 - Google Patents

硝基芳烃和烷基或苯基硼酸一步法制备c-n偶联产物 Download PDF

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CN113801037A
CN113801037A CN202110976337.6A CN202110976337A CN113801037A CN 113801037 A CN113801037 A CN 113801037A CN 202110976337 A CN202110976337 A CN 202110976337A CN 113801037 A CN113801037 A CN 113801037A
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蔡星伟
宋恒
沈洋
赵玉媛
周虎
宋华
丁丹丽
马腾
王浩
徐晨
刘星余
侯苏玉
许琦
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Jingfeng Technology Zhoushan Co ltd
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Zhenjiang Ruifu Intelligent Technology Co ltd
Jiangsu University of Science and Technology
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Abstract

本发明公开了硝基芳烃和烷基或苯基硼酸一步法制备C‑N偶联产物,所述方法将硝基芳烃、烷基或苯基硼酸、还原剂、催化剂均加至极性溶剂中,然后置于反应器内,室温光照条件反应,反应过程中采用TLC薄层色谱跟踪反应进程,最终经柱层析获得偶联产物。与现有技术相比,本发明具有以下优点:(1)本发明所述方法以商品化、价低的硝基芳烃为氮源,以有机硼酸为底物,在还原剂和催化剂存在条件下一步反应合成系列新型C‑N偶联产物,为传统方法难以合成的有机胺类化合物提供了一种实用的方法;(2)所述反应是在室温条件下进行,因此反应条件温和、方法操作简单、经济高效、产率高,具有重要的应用价值。

Description

硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物
技术领域
本发明属于有机化学技术领域,涉及一种通过有机合成方法制备系列化合物的技术,具体为硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物。
背景技术
钯催化芳基卤化物的布赫瓦尔德-哈特威格胺化和铜催化的乌尔曼偶联已成为现代有机化学中最广泛使用的反应之一,且前者是药物化学中最常用的20个反应之一。近几年,随着光化学策略的出现,大大提高了C-N交叉偶联的效率和范围。虽然这些开创性的工作为进一步发展C-N偶联提供了创新的思路,但迄今为止报道的所有构筑多级胺类化合物大多使用胺,特别是苯胺,作为氮源。而胺类化合物通常经过硝基化合物的还原获得。如果将硝基芳烃作为氮源,这样将扩大C-N偶联的适用范围,绕过硝基芳烃还原为胺的步骤,同时潜在地改善偶联中官能团的相容性。虽然硝基化合物与苯基硼酸的偶联已有报道,但是还存在反应温度高(>100℃)、底物适用范围有限等问题。
发明内容
解决的技术问题:为了克服现有技术的不足,获得一种经济的C-N偶联产物合成路线,本发明提供了一种在室温条件下实现硝基芳烃和烷基或苯基硼酸经一步反应制得系列C-N偶联产物的方法。
技术方案:硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物,所述方法将硝基芳烃、烷基或苯基硼酸、还原剂、催化剂均加至极性溶剂中,然后置于反应器内,室温光照条件反应,反应过程中采用TLC薄层色谱跟踪反应进程,最终经柱层析获得偶联产物;
硝基芳烃的结构式如式1所示:
Figure BDA0003227697650000011
苯基硼酸的结构式如式2所示,烷基硼酸的结构式如式3所示:
Figure BDA0003227697650000021
由苯基硼酸制得的偶联产物结构式如式4所示,由烷基硼酸制得的偶联产物结构式如式5所示:
Figure BDA0003227697650000022
其中,R1为-Br、-Cl、-Et、-COOMe、-CF3、-CHO或-COOMe,且R1在苯环上任一位置;X为碳原子或氮原子,且X在苯环上任一位置;R2为-H、-CH3、-OPh、-COOMe或-OCH3;R3为-iPr、-Cy、环丙基、环戊基或-nBu。
优选的,一步法反应方程式为式(1)或式(2):
Figure BDA0003227697650000023
优选的,硝基芳烃、烷基或芳基硼酸、还原剂、催化剂的摩尔比为0.5:0.75-1:1-2:0.05-0.20。
优选的,还原剂为苯基硅烷、二苯基硅烷、三乙氧基硅烷、三苯基膦、三环己基膦、三甲基膦或三乙氧基膦。
优选的,催化剂为钨盐或钨氧化物。
优选的,催化剂为WCl6、WCl4、WCl5、WO3或W(CO)6
优选的,极性溶剂为乙醚、四氢呋喃、环戊己甲醚、甲醇、乙醇、异丙醇或甲苯。
优选的,反应条件具体为:紫外线灯波长为254-500nm,反应时间为24-48小时。
由以上任一所述方法制备获得的C-N偶联产物。
优选的,所述产物的化学式为:
不同硝基底物范围
Figure BDA0003227697650000031
不同硼酸底物范围
Figure BDA0003227697650000041
有益效果:(1)本发明所述方法以商品化、价低的硝基芳烃为氮源,以有机硼酸为底物,在还原剂和催化剂存在条件下一步反应合成系列新型C-N偶联产物,为传统方法难以合成的有机胺类化合物提供了一种实用的方法;(2)所述反应是在室温条件下进行,因此反应条件温和、方法操作简单、反应温和、经济高效、产率高,具有重要的应用价值。
附图说明
图1是实施例8制得的偶联产物12液相扩散培养晶体的X-射线单晶结构图;
图2是实施例12制得的偶联产物34液相扩散培养晶体的X-射线单晶结构图;
图3是化合物3的核磁共振氢谱(400M,CDCl3,25℃);
图4是化合物3的核磁共振碳谱(126MHz,CDCl3,25℃);
图5是化合物5的核磁共振氢谱(400M,CDCl3,25℃);
图6是化合物5的核磁共振碳谱(126MHz,CDCl3,25℃);
图7是化合物7的核磁共振氢谱(400M,CDCl3,25℃);
图8是化合物7的核磁共振碳谱(126MHz,CDCl3,25℃);
图9是化合物10的核磁共振氢谱(400M,CDCl3,25℃);
图10是化合物10的核磁共振碳谱(126MHz,CDCl3,25℃);
图11是化合物12的核磁共振氢谱(400M,CDCl3,25℃);
图12是化合物12的核磁共振碳谱(126MHz,CDCl3,25℃);
图13是化合物21的核磁共振氢谱(400M,CDCl3,25℃);
图14是化合物21的核磁共振碳谱(126MHz,CDCl3,25℃);
图15是化合物23的核磁共振氢谱(400M,CDCl3,25℃);
图16是化合物23的核磁共振碳谱(126MHz,CDCl3,25℃);
图17是化合物30的核磁共振氢谱(400M,CDCl3,25℃);
图18是化合物30的核磁共振碳谱(126MHz,CDCl3,25℃);
图19是化合物37的核磁共振氢谱(400M,CDCl3,25℃);
图20是化合物37的核磁共振碳谱(126MHz,CDCl3,25℃)。
具体实施方式
以下实施例进一步说明本发明的内容,但不应理解为对本发明的限制。在不背离本发明精神和实质的情况下,对本发明方法、步骤或条件所作的修改和替换,均属于本发明的范围。若未特别指明,实施例中所用的技术手段为本领域技术人员所熟知的常规手段。
实施例1
碳氮偶联产物,通式为:
Figure BDA0003227697650000051
具体结构可以是:
不同硝基底物范围
Figure BDA0003227697650000061
不同硼酸底物范围
Figure BDA0003227697650000071
其中,化合物3、5、7、10、12、21、23、30、37的核磁共振氢谱、碳谱结果如图3-20所示。
实施例2
偶联产物1的制备:在氮气氛围中,向10mL的反应管中加入0.5mmol 2-氯-5-硝基嘧啶、0.75mmol苯硼酸、1mmol三苯基膦、0.05mmol WCl6、6mL环戊己甲醚,然后使用双排管将反应管抽真空再通入氮气,此操作重复三次后,在磁力搅拌下用365nm紫外灯光照,反应24小时。结束光照,将反应液移入烧瓶,用二氯甲烷清洗反应管,再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶,旋干。旋干后用乙酸乙酯和石油醚(1:5,v:v)为洗脱剂,柱层析后得纯产品1,产率90%。
实施例3
偶联产物3的制备:在氮气氛围中,向10mL的反应管中加入0.5mmol 5-硝基吡啶甲腈、0.75mmol苯硼酸、1mmol苯基硅烷、0.05mmol WO3、6mL四氢呋喃,然后使用双排管将反应管抽真空再通入氮气,此操作重复三次后,在磁力搅拌下用410nm紫外灯光照,反应24小时。结束光照,将反应液移入烧瓶,用二氯甲烷清洗反应管,再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶,旋干。旋干后用乙酸乙酯和石油醚(1:10,v:v)为洗脱剂,柱层析后得纯产品3,产率92%。
实施例4
偶联产物5的制备:在氮气氛围中,向10mL的反应管中加入0.5mmol 5-硝基吡啶甲醛、0.75mmol苯硼酸、1mmol三乙氧基硅烷、0.05mmol W(CO)6、6mL乙醚,然后使用双排管将反应管抽真空再通入氮气,此操作重复三次后,在磁力搅拌下用400nm紫外灯光照,反应24小时。结束光照,将反应液移入烧瓶,用二氯甲烷清洗反应管,再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶,旋干。旋干后用乙酸乙酯和石油醚(1:20,v:v)为洗脱剂,柱层析后得纯产品5,产率89%。
实施例5
偶联产物7的制备:在氮气氛围中,向10mL的反应管中加入0.5mmol 2-甲基-5-硝基吡啶、0.75mmol苯硼酸、1mmol三苯基膦、0.05mmol WCl5、6mL环戊己甲醚,然后使用双排管将反应管抽真空再通入氮气,此操作重复三次后,在磁力搅拌下用254nm紫外灯光照,反应24小时。结束光照,将反应液移入烧瓶,用二氯甲烷清洗反应管,再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶,旋干。旋干后用乙酸乙酯和石油醚(1:15,v:v)为洗脱剂,柱层析后得纯产品7,产率82%。
实施例6
偶联产物9的制备:在氮气氛围中,向10mL的反应管中加入0.5mmol 1,2,4-三氯-5-硝基苯、0.75mmol苯硼酸、1mmol三苯基膦、0.05mmol WO3、6mL环戊己甲醚,然后使用双排管将反应管抽真空再通入氮气,此操作重复三次后,在磁力搅拌下用254nm紫外灯光照,反应36小时。结束光照,将反应液移入烧瓶,用二氯甲烷清洗反应管,再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶,旋干。旋干后用乙酸乙酯和石油醚(1:50,v:v)为洗脱剂,柱层析后得纯产品9,产率95%。
实施例7
偶联产物11的制备:在氮气氛围中,向10mL的反应管中加入0.5mmol 4-氟-2-硝基-9H-芴、0.75mmol苯硼酸、1mmol苯基硅烷、0.05mmol WCl4、6mL环戊己甲醚,然后使用双排管将反应管抽真空再通入氮气,此操作重复三次后,在磁力搅拌下用365nm紫外灯光照,反应48小时。结束光照,将反应液移入烧瓶,用二氯甲烷清洗反应管,再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶,旋干。旋干后用乙酸乙酯和石油醚(1:100,v:v)为洗脱剂,柱层析后得纯产品11,产率93%。
实施例8
偶联产物12的制备:在氮气氛围中,向10mL的反应管中加入0.5mmol 6-硝基异苯并呋喃-1(3H)-one、0.75mmol苯硼酸、1mmol三苯基膦、0.05mmol WCl6、6mL甲苯,然后使用双排管将反应管抽真空再通入氮气,此操作重复三次后,在磁力搅拌下用400nm紫外灯光照,反应24小时。结束光照,将反应液移入烧瓶,用二氯甲烷清洗反应管,再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶,旋干。旋干后用乙酸乙酯和石油醚(1:100,v:v)为洗脱剂,柱层析后得纯产品12,产率90%。该产品可通过液相扩散法培养其晶体,X-射线单晶结构如图1所示。
实施例9
偶联产物15的制备:在氮气氛围中,向10mL的反应管中加入0.5mmol 1-硝基-3,5-双(三氟甲基)苯、0.75mmol苯硼酸、1mmol三苯基膦、0.05mmol WO3、6mL异丙醇,然后使用双排管将反应管抽真空再通入氮气,此操作重复三次后,在磁力搅拌下用254nm紫外灯光照,反应35小时。结束光照,将反应液移入烧瓶,用二氯甲烷清洗反应管,再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶,旋干。旋干后用乙酸乙酯和石油醚(1:100,v:v)为洗脱剂,柱层析后得纯产品15,产率88%。
实施例10
偶联产物23的制备:在氮气氛围中,向10mL的反应管中加入0.5mmol 4-氯硝基苯、0.75mmol(4-苯甲酰基苯基)硼酸、1mmol三苯基硅烷、0.05mmol WCl6、6mL环戊己甲醚,然后使用双排管将反应管抽真空再通入氮气,此操作重复三次后,在磁力搅拌下用365nm紫外灯光照,反应24小时。结束光照,将反应液移入烧瓶,用二氯甲烷清洗反应管,再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶,旋干。旋干后用乙酸乙酯和石油醚(1:100,v:v)为洗脱剂,柱层析后得纯产品23,产率86%。
实施例11
偶联产物33的制备:在氮气氛围中,向10mL的反应管中加入0.5mmol 4-氯硝基苯、0.65mmol环戊基硼酸、1.3mmol三苯基膦、0.02mmol W(CO)6、6mL乙醚,然后使用双排管将反应管抽真空再通入氮气,此操作重复三次后,在磁力搅拌下用254nm紫外灯光照,反应36小时。结束光照,将反应液移入烧瓶,用二氯甲烷清洗反应管,再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶,旋干。旋干后用乙酸乙酯和石油醚(1:50,v:v)为洗脱剂,柱层析后得纯产品33,产率90%。
实施例12
偶联产物34的制备:在氮气氛围中,向10mL的反应管中加入0.5mmol 4-氯硝基苯、0.75mmol 5-吲哚硼酸、1.2mmol三苯基膦、0.04mmol WCl6、6mL乙醇,然后使用双排管将反应管抽真空再通入氮气,此操作重复三次后,在磁力搅拌下用400nm紫外灯光照,反应48小时。结束光照,将反应液移入烧瓶,用二氯甲烷清洗反应管,再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶,旋干。旋干后用乙酸乙酯和石油醚(1:100,v:v)为洗脱剂,柱层析后得纯产品34,产率92%。该产品可通过液相扩散法培养其晶体,X-射线单晶结构如图2所示。
实施例13
偶联产物37的制备:在氮气氛围中,向10mL的反应管中加入0.5mmol 4-氯硝基苯、0.75mmol环己基硼酸、1.5mmol三苯基膦、0.01mmol WCl4、6mL环戊己甲醚,然后使用双排管将反应管抽真空再通入氮气,此操作重复三次后,在磁力搅拌下用400nm紫外灯光照,反应36小时。结束光照,将反应液移入烧瓶,用二氯甲烷清洗反应管,再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶,旋干。旋干后用乙酸乙酯和石油醚(1:100,v:v)为洗脱剂,柱层析后得纯产品37,产率85%。

Claims (10)

1.硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物,其特征在于,所述方法将硝基芳烃、烷基或苯基硼酸、还原剂、催化剂均加至极性溶剂中,然后置于反应器内,室温光照条件反应,反应过程中采用TLC薄层色谱跟踪反应进程,最终经柱层析获得偶联产物;
硝基芳烃的结构式如式1所示:
Figure FDA0003227697640000011
苯基硼酸的结构式如式2所示,烷基硼酸的结构式如式3所示:
Figure FDA0003227697640000012
由苯基硼酸制得的偶联产物结构式如式4所示,由烷基硼酸制得的偶联产物结构式如式5所示:
Figure FDA0003227697640000013
其中,R1为-Br、-Cl、-Et、-COOMe、-CF3、-CHO或-COOMe,且R1在苯环上任一位置;X为碳原子或氮原子,且X在苯环上任一位置;R2为-H、-CH3、-OPh、-COOMe或-OCH3;R3为-iPr、-Cy、环丙基、环戊基或-nBu。
2.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物,其特征在于,一步法反应方程式为式(1)或式(2):
Figure FDA0003227697640000014
3.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物,其特征在于,硝基芳烃、烷基或芳基硼酸、还原剂、催化剂的摩尔比为0.5:0.75-1:1-2:0.05-0.20。
4.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物,其特征在于,还原剂为苯基硅烷、二苯基硅烷、三乙氧基硅烷、三苯基膦、三环己基膦、三甲基膦或三乙氧基膦。
5.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物,其特征在于,催化剂为钨盐或钨氧化物。
6.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物,其特征在于,催化剂为WCl6、WCl4、WCl5、WO3或W(CO)6
7.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物,其特征在于,极性溶剂为乙醚、四氢呋喃、环戊己甲醚、甲醇、乙醇、异丙醇或甲苯。
8.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物,其特征在于,反应条件具体为:紫外线灯波长为254-500nm,反应时间为24-48小时。
9.由权利要求1-8任一所述方法制备获得的C-N偶联产物。
10.根据权利要求9所述的C-N偶联产物,其特征在于,所述产物的化学式为:
不同硝基底物范围
Figure FDA0003227697640000021
不同硼酸底物范围
Figure FDA0003227697640000031
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