CN110804013B - 一种邻位二胺类化合物的合成方法 - Google Patents

一种邻位二胺类化合物的合成方法 Download PDF

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CN110804013B
CN110804013B CN201910955869.4A CN201910955869A CN110804013B CN 110804013 B CN110804013 B CN 110804013B CN 201910955869 A CN201910955869 A CN 201910955869A CN 110804013 B CN110804013 B CN 110804013B
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毛建友
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings

Abstract

本发明涉及有机合成技术领域，具体公开了一种邻位二胺类化合物的合成方法，反应方程式为：

Description

一种邻位二胺类化合物的合成方法
技术领域
本发明涉及有机合成技术领域，具体涉及一种邻位二胺类化合物的合成方法。
背景技术
邻位二胺类化合物及其衍生物是一类重要的有机分子骨架，广泛存在于化工原料和药物活性分子中。目前此类化合物的合成方法主要有以下几种。
第一种，以烯烃为原料，在铁催化下，采用三甲基硅基叠氮为氮源，得到双叠氮产物，再经还原剂还原得到目标产物，反应式如下(Shou-JieShen,Cheng-Liang,ZhuDeng-Fu,LuHaoXu；ACS Catal.2018,85,4473-4482)：
第二种，以亚胺为原料，在碘化钐(SmI2)及六甲基磷酰三胺(HMPA)的存在下，二聚成为邻二胺中间体，经盐酸甲醇溶液酸解得到目标产物，反应式如下(Yu-WuZhong，KenjiIzumi，Ming-HuaXu，Guo-Qiang Lin，Org.Lett.2004，625，4747-4750)：
第三种，以苯胺、乙烯基乙醚和硝基烷烃为原料，在钯催化剂催化下得到硝基化合物中间体，再经还原反应得到目标产物。反应式如下(Lu Ouyang，Lingzhi Zhan，JianxiaoLi，Qiaoyu Zhang，Chaorong Qi，Wanqing Wu，Huanfeng Jiang，Org.Lett.2018，203，550-553)：
第四种，以氮杂三元环和伯/仲胺为原料，经加热得到目标产物。反应式如下(Yi-Yong Huang,Zong-Chao Lv,Xing Yang,Zhao-Lei Wang,Xiao-XueZou,Zhen-Ni Zhao，FeiChen，Green Chem.,2017,19,924-927)：
对以上四种合成方法进行分析可知，第一种合成方法由于叠氮化合物合成困难，具有潜在的爆炸危险，大大限制了该方法的应用，并且此方法也不适用于工业化大量生产。第二种方法和第三种方法都用到了贵金属催化剂，增加了生产成本，且由于大量的金属残留和大量的固体废物，给化合物的纯化和环保带来非常大的压力。同时，硝基类或卤代类反应底物也非常昂贵，也是限制以上两种方法应用的一个不可忽视的原因。第四种方法的原料难于合成。
因此，开发新的邻位二胺类化合物及其衍生物的合成工艺，以替代以上现有的合成工艺，对实现邻位二胺类化合物及其衍生物的工业化生产具有重要意义。
发明内容
本发明解决的技术问题是提供一种邻位二胺类化合物的合成方法，不需要使用贵金属催化剂，具有原料便宜易得、生产操作简单的优点。
为解决上述技术问题，本发明采用以下技术方案：一种邻位二胺类化合物的合成方法，反应方程式为：
式(Ⅰ)中，
R1任选自苯基、取代苯基、萘基、吡啶基、噻吩基、喹啉基、苯并呋喃基，其中取代苯基的取代基任选自甲基、甲氧基、卤素、三氟甲氧基、苯基、吡啶基、噻吩基、吡咯基；
R2、R3任选自吗啡啉基、硫代吗啉基、哌啶基、1-甲基哌嗪基、甲基、乙基、苄基；
R4任选自吡啶基、异喹啉基；
式(Ⅰ)所示化合物的合成方法：式(2)所示的化合物和式(3)所示的化合物，在碱存在的条件下，反应生成式(Ⅰ)所示邻位二胺类化合物；
反应所用的碱为二(三甲基硅基)氨基锂，二(三甲基硅基)氨基钠和二(三甲基硅基)氨基钾中的一种或多种。
作为一种优选的实施方式，反应时还需要加入添加剂，所用的添加剂为五甲基二乙烯三胺(PMDTA)和/或四甲基乙二胺(TMEDA)。加入添加剂可以提升收率，dr值(非对映体比值)也升高。
可选地，反应时所用的溶剂为四氢呋喃、异丙醚、乙醚、乙二醇二甲醚、叔丁基甲醚、环戊基甲醚中的任一种或多种。
进一步优选地，所述溶剂为异丙醚。
作为一种优选的实施方式，所述反应物的摩尔比为：式(2)所示的化合物:式(3)所示的化合物:碱＝1:(0.75～1.5):2。
作为一种优选的实施方式，所述反应物的摩尔比为：式(2)所示的化合物:式(3)所示的化合物:碱:添加剂＝1:(0.75～1.5):2:1。
作为一种优选的实施方式，反应温度为0～50℃，优选为10℃。
作为一种优选的实施方式，反应时间为6～24h，优选为12h。
本发明的有益效果是：本发明提供了一种新的邻位二胺类化合物的合成方法，采用一锅法合成了邻位二胺类化合物，减少了反应步骤，提高了产物收率；本发明提供的合成方法所用原料简单经济，不使用过渡金属催化剂，更加经济、绿色环保；操作步骤较为简便，无需极端的升温或降温，更易于操作和控制；本发明方法的底物适应性广，可以用于多种邻位二胺类化合物的合成。
本发明方法具有原料便宜易得，生产操作简单，不需要贵金属，环保安全的优点。大大降低了生产成本，同时，实验操作简单，可开发为工业化生产方法。
本发明对合成条件，例如反应溶剂、所用碱、添加剂、以及反应温度和时间等进行了筛选优化，进一步提高了反应收率。
具体实施方式
下面通过实施例，对本发明的技术方案进行详细说明。
实施例1
目标化合物的结构式：
在手套箱中将二(三甲基硅基)氨基钠(NaN(SiMe3)2,73.2mg,0.4mmol)与五甲基二乙烯三胺(42μL,0.2mmol)加入微波管中，然后加入异丙醚(2.0mL)和苯甲醛(20.3μL，0.2mmol)；等待10分钟，用微量注射器加入4-(吡啶-2-基甲基)吗啉(26.7mg,0.15mmol)，加盖从手套箱取出，在10℃下反应12小时，升温至室温。启盖并加三滴水淬灭反应，减压去除溶剂，粗产品柱层析分离(石油醚：乙酸乙酯：三乙胺＝10:10：1)，即可得产品2-吗啉代-1-苯基-2-(吡啶-2-基)乙-1-胺(52.1mg，92％收率，非对映体比值dr值6.0:1)。产品的比移值Rf＝0.34(乙酸乙酯：甲醇＝5:1)，产品的氢谱和碳谱核磁共振谱数据分别为：1H NMR(400MHz,CDCl3)δ:8.53(d,J＝5.5Hz,1H),7.43–7.39(m,1H),7.30–7.23(m,2H),7.15–6.98(m,4H),6.79(d,J＝7.7Hz,1H),4.75(d,J＝10.4Hz,1H),3.83–3.65(m,5H),2.79–2.66(m,2H),2.51(dt,J＝8.8,4.0Hz,2H),2.13(s,2H)；13C{1H}NMR(101MHz,CDCl3)δ:155.7,148.7,142.9,135.4,128.0,127.9,126.9,124.8,122.0,77.3,67.7,54.1,49.9。
实施例2
目标化合物的结构式：
用4-甲基苯甲醛(24μL，0.20mmol)代替实施例1中的苯甲醛，其余操作与实施例1相同，最终以73％的收率(43.4mg)以4.2:1的非对映体比值得到2-吗啉代-2-(吡啶-2-基)-1-(对甲苯基)乙-1-胺，产物的比移值Rf＝0.38(乙酸乙酯：甲醇＝5:1)，产物的氢谱和碳谱核磁共振谱数据分别为：1H NMR(400MHz,CDCl3)δ:8.53(d,J＝5.5Hz,1H),7.45–7.41(m,1H),7.14(d,J＝8.1Hz,2H),7.08–7.00(m,1H),6.92(d,J＝7.9Hz,2H),6.81(d,J＝7.7Hz,1H),4.71(d,J＝10.5Hz,1H),3.83–3.64(m,5H),2.77–2.65(m,2H),2.53–2.40(m,5H),2.19(s,3H)；13C{1H}NMR(101MHz,CDCl3)δ:155.7,148.7,139.6,136.5,135.4,128.8,127.9,124.7,122.0,76.5,67.6,53.7,49.9,21.0。
实施例3
目标化合物的结构式：
用4-甲氧基苯甲醛(26μL，0.20mmol)代替实施例1中的苯甲醛，其余操作与实施例1相同，最终以70％的收率(43.8mg)以6.7:1的非对映体比值得到1-(4-甲氧基苯基)-2-吗啉代-2-(吡啶-2-基)乙-1-胺，产物的比移值Rf＝0.31(乙酸乙酯：甲醇＝3:1)，产物的氢谱和碳谱核磁共振谱数据分别为：1H NMR(400MHz,CDCl3)δ:8.53(d,J＝5.7Hz,1H),7.43(t,J＝7.7Hz,1H),7.17(d,J＝8.7Hz,2H),7.06–6.99(m,1H),6.80(d,J＝7.7Hz,1H),6.65(d,J＝8.7Hz,2H),4.70(d,J＝10.5Hz,1H),3.77(m,2H),3.73–3.64(m,6H),2.70(m,2H),2.50(m,2H),2.14(br,2H)；13C{1H}NMR(101MHz,CDCl3)δ:158.4,155.8,148.7,135.4,134.8,129.0,124.8,121.9,113.4,76.8,67.7,55.1,53.3,49.7。
实施例4
目标化合物的结构式：
用4-苯氧基苯甲醛(36μL，0.20mmol)代替实施例1中的苯甲醛，其余操作与实施例1相同，最终以79％的收率(43.8mg)以4.5:1的非对映体比值得到2-吗啉代-1-(4-苯氧基苯基)-2-(吡啶-2-基)乙-1-胺，产物的比移值Rf＝0.44(乙酸乙酯：甲醇＝5:1)，产物的氢谱和碳谱核磁共振谱数据分别为：1H NMR(400MHz,CDCl3)δ:8.54(d,J＝4.8Hz,1H),7.45(m,1H),7.33–7.19(m,4H),7.05(t,J＝6.6Hz,2H),6.90–6.71(m,5H),4.75(d,J＝10.4Hz,1H),3.84–3.64(m,6H),2.78–2.65(m,2H),2.51(m,2H),2.25(br,2H)；13C{1H}NMR(101MHz,CDCl3)δ:157.4,155.9,155.7,148.8,137.9,135.5,129.7,129.4,125.0,123.1,122.1,118.7,118.6,77.4,67.7,53.6,49.9。
实施例5
目标化合物的结构式：
用萘甲醛(31.2mg，0.20mmol)代替实施例1中的苯甲醛，其余操作与实施例1相同，最终以77％的收率(51.3mg)以5.6:1的非对映体比值得到2-吗啉代-1-(萘-2-基)-2-(吡啶-2-基)乙-1-胺，产物的比移值Rf＝0.48(乙酸乙酯：甲醇＝5:1)，产物的氢谱和碳谱核磁共振谱数据分别为：1H NMR(400MHz,CDCl3)δ:8.52(d,J＝6.5Hz,1H),7.73(s,1H),7.70–7.64(m,2H),7.61(d,J＝8.5Hz,1H),7.43(m,1H),7.40–7.32(m,3H),6.97(m,1H),6.80(d,J＝7.7Hz,1H),4.94(d,J＝10.5Hz,1H),3.94–3.67(m,5H),2.85–2.69(m,2H),2.61–2.46(m,2H),2.34(br,2H)；13C{1H}NMR(101MHz,CDCl3)δ:155.4,148.7,140.3,135.5,133.2,132.6,127.8,127.7,127.5,127.2,126.0,125.7,125.5,124.8,122.1,76.4,67.7,54.1,49.8。
实施例6
目标化合物的结构式：
用4-氯苯甲醛(24μL，0.20mmol)代替实施例1中的苯甲醛，其余操作与实施例1相同，最终以80％的收率(50.6mg)以6.0:1的非对映体比值得到1-(4-氯苯基)-2-吗啉代-2-(吡啶-2-基)乙-1-胺，产物的比移值Rf＝0.4(乙酸乙酯：甲醇＝5:1)，产物的氢谱和碳谱核磁共振谱数据分别为：1H NMR(400MHz,CDCl3)δ:8.54(d,J＝5.6Hz,1H),7.46–7.44(m,1H),7.20(d,J＝8.5Hz,2H),7.10–7.04(m,3H),6.78(d,J＝7.7Hz,1H),4.76(d,J＝10.4Hz,1H),3.77(m,2H),3.73–3.66(m,2H),3.64(d,J＝10.4Hz,1H),2.76–2.65(m,2H),2.49(m,2H),2.10(br,2H)ppm；13C{1H}NMR(101MHz,CDCl3)δ:155.3,148.8,141.7,135.7,132.5,129.5,128.2,125.0,122.3,77.5,76.7,67.7,53.5。
参照实施例1的方法，将反应底物进行变化，分别合成了一系列邻位二胺类衍生物，收率均能达到中等以上，证明此方法底物及官能团适用性广，收率良好，反应高效快捷。合成的衍生物具体见下表中实施例7-24所示。表1中的取代基R1-R4为下式(Ⅰ)所示的取代基。
表1
本发明还对反应的条件进行了筛选，部分实验如下。
反应方程式为：
更换不同的碱、溶剂，在添加剂存在和不存在的条件下分别进行了实验，反应温度均为10℃、反应12h。碱的当量为2.0，添加剂的当量为1.0。结果如下表。
表2
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效变换，或直接或间接运用在其他相关的技术领域，均包括在本发明的专利保护范围内。

Claims (2)

1.一种式(Ⅰ)所示邻位二胺类化合物的合成方法，其特征在于，所述合成方法如下：式(2)所示的化合物和式(3)所示的化合物，在碱存在的条件下，反应生成式(Ⅰ)所示邻位二胺类化合物；
反应所用的碱为二(三甲基硅基)氨基锂，二(三甲基硅基)氨基钠和二(三甲基硅基)氨基钾中的一种或多种；反应时还需要加入添加剂，所用的添加剂为五甲基二乙烯三胺和/或四甲基乙二胺；
反应时所用的溶剂为四氢呋喃、异丙醚、乙醚、乙二醇二甲醚、叔丁基甲醚、环戊基甲醚中的任一种或多种；反应物的摩尔比为：式(2)所示的化合物:式(3)所示的化合物:碱＝1:(0.75～1.5):2，式(2)所示的化合物:式(3)所示的化合物:碱:添加剂＝1:(0.75～1.5):2:1；反应温度为0～50℃；反应时间为6～24h，其中式(2)化合物、式(3)化合物和式(Ⅰ)化合物的结构式如下：
上述式(2)化合物、式(3)化合物和式(Ⅰ)化合物中涉及的取代基定义如下：R1任选自苯基、取代苯基、萘基、吡啶基、噻吩基、喹啉基、苯并呋喃基，其中取代苯基的取代基任选自甲基、甲氧基、卤素、三氟甲氧基、苯基、吡啶基、噻吩基、吡咯基；R2、R3任选自吗啡啉基、硫代吗啉基、哌啶基、1-甲基哌嗪基、甲基、乙基、苄基；R4任选自吡啶基、异喹啉基。
2.根据权利要求1所述的式(Ⅰ)所示邻位二胺类化合物的合成方法，其特征在于，所述反应温度为10℃；所述反应时间为12h；所述溶剂为异丙醚。
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CN109608394A (zh) * 2018-12-03 2019-04-12 湖南大学 氮杂芳胺类化合物的合成方法和氮杂芳胺类化合物
CN109912467A (zh) * 2019-03-28 2019-06-21 南昌航空大学 一种2-芳基苯乙胺衍生物的合成方法

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EP2950649B1 (en) * 2013-02-01 2020-03-04 Wellstat Therapeutics Corporation Amine compounds having anti-inflammatory, antifungal, antiparasitic and anticancer activity

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107814729A (zh) * 2017-11-15 2018-03-20 中国科学技术大学 一类手性芳香胺类化合物及其制备方法
CN109608394A (zh) * 2018-12-03 2019-04-12 湖南大学 氮杂芳胺类化合物的合成方法和氮杂芳胺类化合物
CN109912467A (zh) * 2019-03-28 2019-06-21 南昌航空大学 一种2-芳基苯乙胺衍生物的合成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"一级邻二胺的合成";崔毅;《浙江工业大学学报》;第28卷(第2期);第142-148页 *

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