CN107216269A - 羟基化邻菲罗啉铜配合物/o2催化氧化醇和胺交叉偶联合成亚胺的方法 - Google Patents

羟基化邻菲罗啉铜配合物/o2催化氧化醇和胺交叉偶联合成亚胺的方法 Download PDF

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CN107216269A
CN107216269A CN201710352821.5A CN201710352821A CN107216269A CN 107216269 A CN107216269 A CN 107216269A CN 201710352821 A CN201710352821 A CN 201710352821A CN 107216269 A CN107216269 A CN 107216269A
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copper complex
alkohol
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张玲娟
刘捷
张献明
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Shanxi University
Shaanxi Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • C07D213/02—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
    • 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
    • C07D213/24—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 with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical

Abstract

本发明公开了一种羟基化邻菲罗啉铜配合物/O2催化氧化醇和胺交叉偶联合成亚胺的方法，该方法选用经济廉价的羟基化邻菲罗啉铜配合物作为催化剂，绿色的O2作为氧化剂，在常温条件下实现了醇和胺的交叉偶联，避免了碱和昂贵的氮氧自由基的使用，成功的制备了一系列亚胺类化合物。本发明反应选择性高，底物适用范围较广，具有很大的工业应用的潜能。

Description

羟基化邻菲罗啉铜配合物/O2催化氧化醇和胺交叉偶联合成亚 胺的方法
技术领域
本发明属于醇和胺交叉偶联合成亚胺的技术领域，具体涉及一种以羟基化邻菲罗啉铜配合物作为催化剂，绿色的O2作为氧化剂，催化氧化醇和胺交叉偶联反应合成亚胺的方法。
背景技术
亚胺，又称席夫碱，是一类含C＝N不饱和双键的非常重要的有机合成中间体，由于可以发生环化、还原、加成、缩合等有机反应，从而可以进一步构建药物、工业、生物及天然产物。因此，人们对亚胺的合成和应用一直都有很大的兴趣。
传统上，亚胺一般是由羰基化合物(醛或酮)与一级胺缩合而成。该过程中往往都需要脱水剂及路易斯酸作催化剂，而醛、酮通常是由醇选择氧化获得，而且醇比羰基化合物更绿色化，如更广泛的范围、更容易获得、更稳定、更便宜、毒性更小和更容易处理等。因此直接用醇和胺交叉偶联合成亚胺显然是更有实际意义的方法。其中，用绿色的空气或氧气作为氧化剂已被广泛的应用。所用的催化剂主要分为：金属催化剂(Ru、Os、Pd、Pt、Au、Co、Mn、Cu等)、无金属催化剂、光催化剂、仿生催化剂。与贵金属相比，金属铜具有储存丰富、廉价易得、毒性低等特点，所以铜催化剂在合成亚胺反应中得到了广泛关注。
现有方法中用铜盐作催化剂时，往往需要加入额外的有机配体和碱，以及昂贵的氮氧自由基作助催化剂，反应温度高并且反应时间较长，产物的选择性差等，这些都阻碍了其催化体系的实际应用。
除了铜盐外，铜配合物也可用作催化剂。但是反应中仍需再加入额外的碱，高温、较长的反应时间、狭窄的醇底物的范围限制了配合物作催化剂的最终应用。
发明内容
本发明所要解决的技术问题在于提供一种不需要额外加入有机配体、碱、氮氧自由基，在常温条件下高效、快速的实现醇和胺的交叉偶联合成亚胺的方法。
解决上述技术问题所采用的技术方案是：以羟基化邻菲罗啉铜配合物为催化剂，将式1所示的醇与式2所示的胺按摩尔比为1:1.1～1.5加入有机溶剂中，在一个标准大气压的O2气氛中常温反应，得到式3所示的亚胺。
式中R1代表苯基、卤代苯基、烷基取代苯基、烷氧基取代苯基、4-甲硫基苯基、C6H5CH＝CH、环烷基、吡啶基、呋喃基中的任意一种；R2代表苯基、烷基取代苯基、烷氧基取代苯基、烷基、环烷基中的任意一种。
上述的R1优选苯基、卤代苯基、C1～C4烷基取代苯基、C1～C4烷氧基取代苯基、4-甲硫基苯基、C6H5CH＝CH、C5～C6环烷基、吡啶基、呋喃基中的任意一种，R2优选苯基、C1～C4烷基取代苯基、C1～C4烷氧基取代苯基、C4～C6烷基、C5～C6环烷基中的任意一种。
上述的羟基化邻菲罗啉铜配合物的加入量优选为醇摩尔量的2％～3％。
上述的有机溶剂为乙腈、四氢呋喃、N,N-二甲基甲酰胺中的任意一种。
上述的羟基化邻菲罗啉铜配合物(Cu2(ophen)2)根据文献Syntheses,CrystalStructures,and Physical Properties of Dinuclear Copper(I)and TetranuclearMixed-Valence Copper(I,II)Complexes with Hydroxylated Bipyridyl-Like Ligands(Chem.-Eur.J.,2002,8:3187-3194.)中的方法合成，其具有以下两大特点：(1)有配位不饱和的金属中心，分子中存在弱的Cu(I)-Cu(I)成键作用，在适当的条件下，弱的金属-金属键可以被打断，使CuⅠ中心成为催化氧化的活性位点；(2)容易被单电子氧化至CuICuII(ophen)2的混合价态。
本发明采用廉价易得的Cu2(ophen)2作催化剂，以绿色的O2作氧化剂，在室温条件下，即可高效和快速的实现醇和胺的交叉偶联，并且避免了氮氧自由基和碱的使用，反应选择性高，底物适用范围较广，具有很大的工业应用的潜能。
具体实施方式
下面结合实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
将50μL(0.5mmol)苯甲醇、65μL(0.6mmol)卞胺、0.0065g(0.0125mmol)Cu2(ophen)2、2mL DMF依次加入到10mL圆底烧瓶中，在一个标准大气压的O2气氛中常温反应12小时。经气相色谱检测(HP-5毛细管柱，以氮气作载气流速为1.0mL/min，柱温：初始温度40℃(维持4min)，以20℃/min升温至285℃(维持2min)，进样口温度：270℃，检测器器温度：300℃)，苯甲醇的转化率为92％，产物N-苄基苯甲醛亚胺的收率为90％。
实施例2
在实施例1中，所用的苯甲醇用等摩尔4-甲硫基苯甲醇替换，其他步骤与实施例1相同，经气相色谱检测，4-甲硫基苯甲醇的转化率为99％，产物N-苄基-4-甲硫基苯甲醛亚胺的收率为97％。
实施例3
在实施例1中，所用的苯甲醇用等摩尔4-甲氧基苯甲醇替换，其他步骤与实施例1相同，经气相色谱检测，4-甲氧基苯甲醇的转化率为89％，产物N-苄基-4-甲氧基苯甲醛亚胺的收率为88％。
实施例4
在实施例1中，所用的苯甲醇用等摩尔2-甲氧基苯甲醇替换，其他步骤与实施例1相同，经气相色谱检测，2-甲氧基苯甲醇的转化率>99％，产物N-苄基-2-甲氧基苯甲醛亚胺的收率为98％。
实施例5
在实施例1中，所用的苯甲醇用等摩尔4-氯苯甲醇替换，其他步骤与实施例1相同，经气相色谱检测，4-氯苯甲醇的转化率为87％，产物N-苄基-4-氯苯甲醛亚胺的收率为84％。
实施例6
在实施例1中，所用的苯甲醇用等摩尔4-溴苯甲醇替换，其他步骤与实施例1相同，经气相色谱检测，4-溴苯甲醇的转化率为85％，产物N-苄基-4-溴苯甲醛亚胺的收率为84％。
实施例7
在实施例1中，所用的苯甲醇用等摩尔肉桂醇替换，其他步骤与实施例1相同，经气相色谱检测，肉桂醇的转化率为93％，产物N-苄基-肉桂醛亚胺的收率为90％。
实施例8
在实施例1中，所用的苯甲醇用等摩尔3-吡啶甲醇替换，其他步骤与实施例1相同，经气相色谱检测，3-吡啶甲醇的转化率为96％，产物N-苄基-3-吡啶甲醛亚胺的收率为92％。
实施例9
在实施例1中，所用的苯甲醇用等摩尔2-呋喃甲醇替换，其他步骤与实施例1相同，经气相色谱检测，2-呋喃甲醇的转化率为75％，产物N-苄基-2-呋喃甲醛亚胺的收率为70％。
实施例10
在实施例1中，所用的苯甲醇用等摩尔环己甲醇替换，其他步骤与实施例1相同，经气相色谱检测，环己甲醇的转化率为99％，产物N-苄基环己甲醛亚胺的收率为97％。
实施例11
在实施例1中，所用的苄胺用等摩尔正己胺替换，其他步骤与实施例1相同，经气相色谱检测，苯甲醇的转化率为97％，产物N-正己基苯甲醛亚胺的收率为95％。
实施例12
在实施例1中，所用的苄胺用等摩尔环己甲胺替换，其他步骤与实施例1相同，经气相色谱检测，苯甲醇的转化率为98％，产物N-环己基亚甲基苯甲醛亚胺的收率为95％。
实施例13
在实施例1中，所用的苄胺用等摩尔4-甲氧基苄胺替换，其他步骤与实施例1相同，经气相色谱检测，苯甲醇的转化率为83％，产物N-4-甲氧基苄基苯甲醛亚胺的收率为82％。
为了确定本发明的工艺条件发明人进行了大量的实验室研究试验，具体实验情况如下：
将50μL(0.5mmol)苯甲醇、65μL(0.6mmol)卞胺、催化剂、碱、2mL溶剂依次加入到10mL圆底烧瓶中，在空气气氛或氧气气氛中常温反应12小时。采用气相色谱检测(HP-5毛细管柱，以氮气作载气流速为1.0mL/min，柱温：初始温度40℃(维持4min)，以20℃/min升温至285℃(维持2min)，进样口温度：270℃，检测器器温度：300℃)苯甲醇的转化率，结果见表1。
表1 苯甲醇和苄胺交叉偶联反应条件
注：表中NaOH加入量为0.5mmol，phen表述邻菲罗啉。
由表1可见，在溶剂乙腈、THF、DMF中，以Cu2(ophen)2为催化剂，氧气作氧化剂，在无需加入额外碱的情况下，常温反应12小时，苯甲醇和苄胺交叉偶联反应合成N-苄基苯甲醛亚胺，苯甲醇的转化率均可达到90％左右。

Claims (5)

1.一种羟基化邻菲罗啉铜配合物/O2催化氧化醇和胺交叉偶联合成亚胺的方法，其特征在于：以羟基化邻菲罗啉铜配合物为催化剂，将式1所示的醇与式2所示的胺按摩尔比为1:1.1～1.5加入有机溶剂中，在一个标准大气压的O2气氛中常温反应，得到式3所示的亚胺；
式中R1代表苯基、卤代苯基、烷基取代苯基、烷氧基取代苯基、4-甲硫基苯基、C6H5CH＝CH、环烷基、吡啶基、呋喃基中的任意一种；R2代表苯基、烷基取代苯基、烷氧基取代苯基、烷基、环烷基中的任意一种。
2.根据权利要求1所述的羟基化邻菲罗啉铜配合物/O2催化氧化醇和胺交叉偶联合成亚胺的方法，其特征在于：所述的R1代表苯基、卤代苯基、C1～C4烷基取代苯基、C1～C4烷氧基取代苯基、4-甲硫基苯基、C6H5CH＝CH、C5～C6环烷基、吡啶基、呋喃基中的任意一种。
3.根据权利要求1所述的羟基化邻菲罗啉铜配合物/O2催化氧化醇和胺交叉偶联合成亚胺的方法，其特征在于：所述的R2代表苯基、C1～C4烷基取代苯基、C1～C4烷氧基取代苯基、C4～C6烷基、C5～C6环烷基中的任意一种。
4.根据权利要求1～3任意一项所述的羟基化邻菲罗啉铜配合物/O2催化氧化醇和胺交叉偶联合成亚胺的方法，其特征在于：所述的羟基化邻菲罗啉铜配合物的加入量为醇摩尔量的2％～3％。
5.根据权利要求1所述的羟基化邻菲罗啉铜配合物/O2催化氧化醇和胺交叉偶联合成亚胺的方法，所述的有机溶剂为乙腈、四氢呋喃、N,N-二甲基甲酰胺中的任意一种。
CN201710352821.5A 2017-05-18 2017-05-18 羟基化邻菲罗啉铜配合物/o2催化氧化醇和胺交叉偶联合成亚胺的方法 Active CN107216269B (zh)

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QIANG KANG: "Copper-catalyzed highly efficient aerobic oxidative synthesis of imines from alcohols and amines", 《GREEN CHEMISTRY》 *
YUNG-SYUAN LAN ETAL: "Preparation of Imines by Oxidative Coupling of Benzyl Alcohols with Amines Catalysed by Dicopper Complexes", 《EUR. J. ORG. CHEM.》 *
刘捷等: "无碱、无TEMPO 的铜催化醇的需氧氧化", 《中国化学会第九届全国有机化学学术会议》 *

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CN109232308A (zh) * 2018-09-26 2019-01-18 河南师范大学 一种利用铜催化剂催化胺和醇交叉偶联制备亚胺的方法
CN109232308B (zh) * 2018-09-26 2022-11-29 河南师范大学 一种利用铜催化剂催化胺和醇交叉偶联制备亚胺的方法
CN110423201A (zh) * 2019-04-30 2019-11-08 郑州大学 一种以己内酰胺为原料合成己二胺的方法

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