CN117466744A - 一种光化学铁催化合成芳胺类化合物的方法 - Google Patents

一种光化学铁催化合成芳胺类化合物的方法 Download PDF

Info

Publication number
CN117466744A
CN117466744A CN202311448033.8A CN202311448033A CN117466744A CN 117466744 A CN117466744 A CN 117466744A CN 202311448033 A CN202311448033 A CN 202311448033A CN 117466744 A CN117466744 A CN 117466744A
Authority
CN
China
Prior art keywords
iron
photochemical
steps
nmr
aromatic amine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311448033.8A
Other languages
English (en)
Inventor
薛东
宋戈洋
李琪
农定展
宋佳萌
黄柠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi Normal University
Original Assignee
Shaanxi Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi Normal University filed Critical Shaanxi Normal University
Priority to CN202311448033.8A priority Critical patent/CN117466744A/zh
Publication of CN117466744A publication Critical patent/CN117466744A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate 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
    • C07D205/00—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D205/02—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D205/04—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C07D215/42—Nitrogen atoms attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/20—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/0832—Other preparations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种光化学铁催化合成芳胺类化合物的方法，以廉价且来源丰富的芳基溴化物和胺类化合物作为反应原料，以廉价铁盐为催化剂、联吡啶为配体，同时添加有机碱，在氩气氛围中通过光激发铁催化芳基溴化物和胺类化合物的C‑N偶联反应实现了芳胺类化合物的合成。本发明反应体系简单、操作简便、反应条件温和，后处理简单，目标化合物选择性好、收率高，避免了传统的昂贵金属催化剂以及无机碱的使用造成催化体系反应复杂、官能团兼容性差等问题，具有很好的应用价值和市场前景。

Description

一种光化学铁催化合成芳胺类化合物的方法
技术领域
本发明属于芳胺类化合物的合成技术领域，具体涉及一种通过光化学铁催化合成芳胺类化合物的方法。
背景技术
过渡金属催化的C-N偶联反应被广泛地应用于药物和精细化学品的合成，被列为现代药物合成中20种最常用的反应之一(Org.Process Res.Dev.2014,18,1752，Org.Process Res.Dev.2019,23,1529)。基于配体调控策略，钯、镍催化的Buchwald-Hartwig胺化反应(Chem.Soc.Rev.2011,40,5068)、铜催化的Ullmann-Ma偶联反应(Chin.J.Chem.2020,38,879)得到了快速发展，为芳胺类化合物的高效合成提供了重要方法。尽管钯、镍和铜催化的偶联反应方面取得了重大进展，仍然需要发展廉价且环保的催化新方法。
铁是地球上储量丰度最高的过渡金属，而且各种铁盐和铁配合物可大规模获得并且价格低廉；同时，铁具有良好的生物兼容性，是人体必需的一种微量元素，以铁配合物为核心的金属蛋白质参与了多种重要的生命过程，因此发展铁为金属催化剂具有很好的潜力(Chem.Soc.Rev.2008,37,1108)。事实上，在过去的几十年里，铁作为催化剂已经取得了诸多令人瞩目的研究进展，被成功应用于多种化学转化。自1971年，Tamura和Kochi的开创性铁催化偶联反应发展以来，铁盐已成为许多有机转化的替代和有前途的催化剂(J.Chem.Soc.,Chem.Commun.1972,144)。因此，发展铁催化C-N偶联反应是一种绿色、可持续的新途径。2007年，Bolm(Angew.Chem.Int.Ed.2007,46,8862)课题组使用双齿氮配体(DMEDA)，实现了首例铁催化芳基卤化物与N-亲核试剂的C-N偶联反应。接着，Tao(Adv.Synth.Catal.2009,351,720)和Kwang(Tetrahedron Lett.2009,50,5868)、Liu(Org.Lett.2008,10,4513)、Paul(Inorg.Chem.2019,58,1935)等人发展了脯氨酸和菲啰啉等为配体的芳基碘化物与N-亲核试剂(吡唑、吲哚等)的C-N偶联反应。为了提高铁催化芳基C-N键的高效构建，Taillefer(Angew.Chem.Int.Ed.2007,46,934)、Wakharkar(Catal.Commun.2007,8,65)、Liu(Green Chem.2010,12,276)等小组发展了Fe/Cu-双金属催化的C-N偶联反应。通过发展双齿氮配体的策略，铁催化的C-N偶联反应得到了发展，然而铁催化的C-N偶联反应通常需要高温(>100℃)、无机碱等造成官能团兼容性差，底物的适用范围有限等问题。最重要的是，Bolm和Buchwald发现铁催化的C-N偶联中微量残留的铜是主要的催化活性的物质(Chem.Soc.Rev.2012,41,979)。在此之后，使得铁催化的C-N偶联反应几乎停滞不前。
近年来，光促进有机合成反应被认为是环境友好、清洁以及可持续性的化学转化过程(Asian J.Org.Chem 2020,9,1519)。将光催化与铁催化结合，为有机合成中碳-碳键或碳-杂键的构建提供了一种新的研究策略。最近，铁催化在构建C-杂原子键的反应中取得了一些重要的研究进展。2012年，Bao(Chem.Commun.2023,59,752)课题组报道了可见光诱导铁催化的α-氨基酸与二恶唑酮的脱羧C-N偶联反应得到酰胺衍生物。2022年，Zeng(ACSCatal.2021,11,13955)课题组报道了在无光敏剂条件下，廉价的铁络合物作为催化剂，醛或苄醇与硝基芳烃在无强氧化剂或还原剂下得到酰胺衍生物。2022年，Bao(Org.Lett.2022,24,4766)课题组在无光敏剂条件下，有效地实现了光诱导铁催化芳基硼酸和二恶唑酮芳基C-N偶联反应。然而，在光与铁催化的C-N偶联反应中，以来源丰富廉价易得的芳基卤化物为亲电试剂与N-亲核试剂偶联反应的研究较少，主要原因是铁催化剂进行氧化加成通常需要低价态，高价铁催化剂进行氧化加成时比较困难。因此，调控Fe催化剂产生低价铁活性物种与芳基卤化物的氧化加成，有可能是促进芳基C-N偶联反应的关键。因此，发展使用简单易得配体，通用性的高效芳基溴化物与胺类的C-N偶联仍然十分重要。
发明内容
本发明的目的是提供一种使用廉价的铁盐与联吡啶催化体系，实现芳基溴化物与胺类化合物的C-N偶联，合成芳胺类化合物的方法。
针对上述目的，本发明所采用的技术方案是：将式I所示芳基溴化物与式II所示胺类化合物、联吡啶、铁催化剂、有机碱加入有机溶剂中，在氩气氛围中加热并光照反应，反应完后分离纯化产物，得到式III所示芳胺类化合物；
式中，Ar代表芳基、取代芳基、杂环芳基、取代杂环芳基中任意一种，具体如：苯基、噻吩基、噻唑基、吡啶基、吡唑基、哌啶基、吡嗪基、喹啉基、苯丙噻吩基、苯并呋喃基、二苯并噻吩基、喹喔啉基中任意一种，或者含C1～C6烷基、C6～环烷基、叔丁基二甲基硅氧基、磺酰基、吖啶基、哌啶基、三甲基甲硅烷基、卤素、C1～C4烷氧基、三氟甲氧基、三氟甲基、氰基、酯基、醛基、酰基、羰基、硼酯基中至少1种取代基的苯基；HNNu代表芳胺、取代芳胺、杂环芳胺、吡唑、酰胺、磺酰胺、脂肪胺中任意一种。
上述合成方法中，优选胺类化合物的用量为芳基溴化物摩尔量的1.1～2倍。
上述合成方法中，优选联吡啶的用量为芳基溴化物摩尔量的5％～20％。
上述合成方法中，优选铁催化剂为溴化亚铁、碳酸亚铁、醋酸亚铁、氯化亚铁等中任意一种，其用量为芳基溴化物摩尔量的5％～15％。
上述合成方法中，优选有机碱为1,8-二氮杂二环十一碳-7-烯(DBU)、四甲基胍(TMG)、7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯(MTBD)、1,2-二甲基-1,4,5,6-四氢嘧啶(DMTHPM)等中任意一种，其用量为芳基溴化物摩尔量的2～3倍。
上述合成方法中，优选有机溶剂为二甲基亚砜、甲苯、异丙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中任意一种或两种。
上述合成方法中，优选在氩气氛围中，在波长为360～430nm的紫外光照射下80～90℃反应24～48小时。
本发明的有益效果如下：
本发明使用廉价的铁盐与联吡啶催化体系，在光照条件下实现芳基溴化物与胺类化合物C-N偶联反应合成芳胺类化合物。本发明反应体系简单，反应经济效益较高、对环境无害，反应后处理简单，芳胺类化合物具有收率好、官能团兼容性优异等优点，是一种简单、高效合成芳胺类化合物的方法，与目前追求环保、经济、绿色的化学概念相符合，具有非常重要的应用前景。
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并不仅限于这些实施例。
实施例1
在氩气氛围中，将31.4mg(0.2mmol)溴苯、29.4mg(0.4mmol)正丁胺、1.9mg(0.01mmol)联吡啶、3.5mg(0.01mmol)碳酸亚铁、67.4mg(0.6mmol)DMTHPM、2mL N,N-二甲基甲酰胺、磁子加入反应管中，在波长为390～395nm的紫外光照射下，85℃反应36小时。反应完后冷却至室温，加入饱和氯化钠水溶液和乙酸乙酯稀释萃取得到有机相，减压蒸馏有机相得到粗产物，以石油醚与乙酸乙酯体积比为100:1至10:1的混合液为淋洗剂，柱层析分离粗产物，得到结构式如下的淡黄色油状产物，其产率为95％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.17(t,J＝7.6Hz,2H),6.69(dd,J＝7.6,7.0Hz,1H),6.61(d,J＝8.4Hz,2H),3.12(t,J＝7.1Hz,2H),1.65-1.60(m,2H),1.49-1.39(m,2H),0.96(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ148.7,129.4,117.2,112.9,43.8,31.9,20.5,14.0；HRMS(ESI)m/z C10H16N[M+H]+:理论值150.1277,实测值150.1279。
实施例2
本实施例中，用等摩尔4-溴苯-(三甲基甲硅烷基)苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为70％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.38(d,J＝7.7Hz,2H),6.66(d,J＝7.9Hz,2H),3.69(br,1H),3.17(m,2H),1.69-1.61(m,2H),1.53-1.42(m,2H),1.01(t,J＝7.3Hz,3H),0.28(s,9H)；13C NMR(100MHz,CDCl3)δ134.6,129.3,112.8,112.3,43.5,31.8,20.4,14.0,-0.7；HRMS(ESI)m/z C13H24NSi[M+H]+:理论值222.1673,实测值222.1671。
实施例3
本实施例中，用等摩尔4-溴苯硼酸频呐醇酯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色固体产物，其产率为78％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.56(d,J＝6.6Hz,2H),6.50(d,J＝3.2Hz,2H),3.15-2.98(m,2H),1.54-1.50(m,2H),1.38-1.30(s,2H),1.26-1.23(m,12H),0.89-0.84(m,3H)；13C NMR(100MHz,CDCl3)δ151.2,136.5,131.1,111.8,83.3,43.3,31.7,29.8,25.0,20.4,14.0；HRMS(ESI)m/z C16H27BNO2[M+H]+:理论值276.2129,实测值276.2125。
实施例4
本实施例中，用等摩尔4-溴二氟甲氧基苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为89％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ6.89(d,J＝8.7Hz,2H),6.47(d,J＝8.6Hz,2H),6.20(t,J＝75.0Hz,1H),3.52(br,1H),3.01(t,J＝7.1Hz,2H),1.63-1.44(m,4H),1.39-1.32(m,3H),0.89(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ146.5,142.2,121.4,117.93(t,J＝258.6Hz),113.1,44.0,31.6,20.3,13.9；19F NMR(376MHz,CDCl3)δ-79.83(s,F),-80.03(s,F)；HRMS(ESI)m/z C11H16F2NO[M+H]+:理论值216.1194,实测值216.1197。
实施例5
本实施例中，用等摩尔N-甲基-4-溴苯甲酰胺替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的白色固体产物，其产率为76％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.61(d,J＝8.7Hz,2H),6.54(d,J＝8.7Hz,2H),6.11(br,1H),4.02(br,1H),3.13(t,J＝7.1Hz,2H),2.96(d,J＝4.8Hz,3H),1.68-1.60(m,2H),1.47-1.40(m,2H),0.96(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ168.2,151.0,128.5,122.5,111.6,43.2,31.5,26.7,20.2,13.9；HRMS(ESI)m/z C12H19N2O[M+H]+:理论值207.1492,实测值207.1496。
实施例6
本实施例中，用等摩尔4-溴氟苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为79％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ6.88(t,J＝8.7Hz,2H),6.56-6.49(m,2H),3.07(t,J＝7.1Hz,2H),1.60(m,2H),1.49-1.37(m,3H),0.96(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ155.6(d,J＝234.4Hz),144.9,115.6(d,J＝22.2Hz),113.4(d,J＝7.4Hz),44.3,31.6,20.3,13.9；19F NMR(376MHz,CDCl3)δ-128.59(s,F)；HRMS(ESI)m/z C10H15NF[M+H]+:理论值168.1183,实测值168.1186。
实施例7
本实施例中，用等摩尔3-氯-5-甲氧基溴苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为76％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ6.28-6.31(m,2H),6.01(d,J＝1.7Hz,1H),3.75(d,J＝1.1Hz,3H),3.07(t,J＝7.0Hz,2H),1.65-1.57(m,2H),1.48-1.39(m,3H),0.96(m,3H)；13C NMR(100MHz,CDCl3)δ161.4,150.5,135.6,105.9,103.0,97.1,55.5,43.6,31.6,20.4,14.0；HRMS(ESI)m/z C11H17NOCl[M+H]+:理论值214.0993,实测值214.0996。
实施例8
本实施例中，用等摩尔2-氟-4-氯溴苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为78％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ6.93-6.82(m,2H),6.50(t,J＝9.1Hz,1H),3.74(br,1H),3.03(t,J＝7.1Hz,2H),1.59-1.47(m,2H),1.38-1.27(m,2H),0.88(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ151.0(d,J＝241.7Hz),135.8(d,J＝11.6Hz),124.5(d,J＝3.5Hz),120.2(d,J＝9.6Hz),115.1(d,J＝22.1Hz),112.3(d,J＝4.3Hz),43.3,31.4,20.2,13.8；HRMS(ESI)m/z C10H14NFCl[M+H]+:理论值202.0793,实测值202.0797。
实施例9
本实施例中，用等摩尔4-溴2-三氟甲基吡啶替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为84％。
所得产物的核磁波谱数据为：1HNMR(600MHz,CDCl3)δ8.33(d,J＝5.1Hz,1H),6.91(s,1H),6.66(d,J＝2.1Hz,1H),5.15(br,1H),3.29(d,J＝5.0Hz,2H),1.80-1.67(m,2H),1.58-1.49(m,2H),1.13-1.03(m,3H)；13C NMR(100MHz,CDCl3)δ154.3,149.9,148.5(q,J＝33.6Hz),121.8(q,J＝274.2Hz),108.8,104.1,42.4,30.8,20.0,13.6；19F NMR(376MHz,CDCl3)δ-68.53(s,CF3)；HRMS(ESI)m/z C10H14F3N2[M+H]+:理论值219.1104,实测值219.1107。
实施例10
本实施例中，用等摩尔2-溴吡嗪替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为81％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.96(s,1H),7.86(s,1H),7.77(s,1H),4.66(br,1H),3.39-3.27(m,2H),1.66-1.54(m,2H),1.48-1.37(m,2H),0.94(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ154.9,142.1,132.7,131.9,41.4,31.7,20.2,13.9；HRMS(ESI)m/z C8H14N3[M+H]+:理论值152.1182,实测值152.1186。
实施例11
本实施例中，用等摩尔4-溴喹啉替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为79％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ8.86(d,J＝3.1Hz,1H),8.15(d,J＝8.5Hz,1H),7.56(t,J＝8.0Hz,1H),7.47(d,J＝8.4Hz,1H),7.31(dd,J＝8.5,4.2Hz,1H),6.63(d,J＝7.6Hz,1H),3.27(t,J＝7.1Hz,2H),1.82-1.69(m,2H),1.59-1.50(m,2H),1.01(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ149.8,149.2,143.8,130.4,128.6,119.2,118.3,118.1,104.5,43.9,31.4,20.4,13.9；HRMS(ESI)m/zC13H17N2[M+H]+:理论值201.1386,实测值201.1389。
实施例12
本实施例中，用等摩尔5-溴苯并噻吩替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为80％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.61(d,J＝8.6Hz,1H),7.35(d,J＝5.4Hz,1H),7.20-7.10(m,1H),6.98(d,J＝2.3Hz,1H),6.72(dd,J＝8.6,2.3Hz,1H),3.62(br,1H),3.24-3.10(m,2H),1.69-1.58(m,2H),1.51-1.43(m,2H),0.97(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ146.1,141.1,129.1,126.7,123.3,122.7,114.0,104.7,44.2,31.7,20.4,13.9；HRMS(ESI)m/z C12H16NS[M+H]+:理论值206.0998,实测值206.0995。
实施例13
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔乙胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为91％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.41(d,J＝8.3Hz,2H),6.59(d,J＝8.3Hz,2H),3.91(br,1H),3.19(q,J＝6.9Hz,2H),1.35-1.24(m,3H)；13C NMR(100MHz,CDCl3)δ150.9,129.3,126.7(q,J＝3.8Hz)；125.2(q,J＝270.2Hz),118.6(q,J＝32.5Hz)；111.8,38.2,14.7；HRMS(ESI)m/z C9H11NF3[M+H]+:理论值190.0838,实测值190.0834。
实施例14
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔丁-3-烯-1-胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为89％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.41(d,J＝8.5Hz,2H),6.60(d,J＝8.5Hz,2H),5.88-5.76(m,1H),5.24-5.10(m,2H),4.01(br,1H),3.22(t,J＝6.1Hz,2H),2.41(q,J＝6.7Hz,2H)；13C NMR(100MHz,CDCl3)δ150.8,135.4,126.6(q,J＝3.8Hz),125.4(q,J＝270.1Hz),118.6(q,J＝32.5Hz),117.6,112.0,42.4,33.5；HRMS(ESI)m/zC11H13NF3[M+H]+:理论值216.0995,实测值216.0998。
实施例15
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔3-甲氧基丙胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为85％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.21(d,J＝7.6Hz,2H),6.58(d,J＝7.7Hz,2H),3.51(t,J＝5.8Hz,2H),3.35(s,3H),3.22(t,J＝6.5Hz,2H),1.96-1.93(m,2H),1.28(s,9H)；13C NMR(100MHz,CDCl3)δ146.2,140.1,126.1,112.6,71.4,58.9,42.1,33.9,31.7,29.6；HRMS(ESI)m/z C14H24NO[M+H]+:理论值222.1852,实测值222.1855。
实施例16
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔2-巯基乙胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为70％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.33(d,J＝8.3Hz,2H),6.56(d,J＝8.3Hz,2H),4.33(br,1H),3.28(t,J＝6.3Hz,2H),2.70(t,J＝6.2Hz,2H),2.04(s,3H)；13C NMR(100MHz,CDCl3)δ150.2,126.7(q,J＝3.8Hz),124.9(q,J＝270.3Hz),119.2(q,J＝32.6Hz),112.1,41.3,33.4,14.9；HRMS(ESI)m/zC10H13F3NS[M+H]+:理论值236.0715,实测值236.0719。
实施例17
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔1-氨基丁醇替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为89％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.39(d,J＝8.4Hz,2H),6.59(d,J＝8.4Hz,2H),3.70(t,J＝5.7Hz,2H),3.18(t,J＝6.4Hz,2H),1.76-1.64(m,4H)；13CNMR(100MHz,CDCl3)δ150.9,126.7(q,J＝3.8Hz),125.3(d,J＝270.3Hz),118.7(q,J＝32.5Hz),111.9,62.6,43.4,30.2,25.9；HRMS(ESI)m/z C11H15F3NO[M+H]+:理论值234.1100,实测值234.1105。
实施例18
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔2-氟乙胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为87％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.41(d,J＝7.8Hz,2H),6.63(d,J＝7.9Hz,2H),4.73-4.44(m,2H),4.29(s,1H),3.59-3.41(m,2H)；13C NMR(100MHz,CDCl3)δ150.1,126.70(q,J＝3.7Hz),124.9(d,J＝270.3Hz),119.6(q,J＝32.9Hz),112.2,82.1(d,J＝168.0Hz),43.7(d,J＝20.4Hz)；HRMS(ESI)m/zC9H10NF4[M+H]+:理论值208.0744,实测值208.0749。
本实施例中，用等摩尔TMG代替MTBD，产物的产率为85％。
实施例19
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔3-三氟甲基丙胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为73％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.43(d,J＝8.5Hz,2H),6.61(d,J＝8.5Hz,2H),3.98(br,1H),3.26(t,J＝7.0Hz,2H),2.30-2.12(m,2H),1.98-1.85(m,2H)；13C NMR(100MHz,CDCl3)δ150.4,126.9(d,J＝276.2Hz),126.6(q,J＝3.7Hz),125.12(q,J＝270.3Hz),119.3(q,J＝32.6Hz),112.0,42.3,31.4(q,J＝29.1Hz),22.1(q,J＝2.4Hz)；HRMS(ESI)m/z C11H12NF6[M+H]+:理论值272.0868,实测值272.0864。
实施例20
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔环丙级胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为89％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.42(d,J＝8.3Hz,2H),6.79(d,J＝8.3Hz,2H),4.44(br,1H),2.46(s,1H),0.79(d,J＝6.2Hz,2H),0.54(s,2H)；13C NMR(100MHz,CDCl3)δ151.3,126.6(q,J＝3.7Hz),126.1(d,J＝276.2Hz),119.3(q,J＝32.7Hz),112.5,25.0,7.7；19F NMR(376MHz,CDCl3)δ-60.96(s,CF3)；HRMS(ESI)m/zC10H11NF3[M+H]+:理论值202.0838,实测值202.0835。
实施例21
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔3,3-二氟环丁胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为83％。
所得产物的核磁波谱数据为：1H NMR(400MHz,DMSO)δ7.21(d,J＝8.6Hz,2H),6.46(d,J＝8.6Hz,2H),3.64(br,1H),3.39 -3.28(m,1H),3.00-2.76(m,2H),2.41-2.19(m,2H)；13C NMR(100MHz,DMSO)δ150.8 126.74(q,J＝3.7Hz),125.2(q,J＝270.1Hz),116.78(q,J＝31.9Hz),112.3,42.59(dd,J＝22.7,21.1Hz),37.09(dd,J＝16.8,7.3Hz),37.09(dd,J＝16.8,7.3Hz)；19F NMR(376MHz,DMSO)δ-59.20(s),-81.05(tq,J＝13.8,6.8Hz),-81.56(dp,J＝20.7,6.8Hz),-93.64--93.93(m),-94.27(ttd,J＝16.4,13.4,3.4Hz)；HRMS(ESI)m/zC11H11NF5[M+H]+:理论值252.0806,实测值252.0803。
实施例22
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔3-氟氮杂环丁烷替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为79％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.29(d,J＝8.6Hz,2H),6.47(d,J＝8.6Hz,2H),5.52-5.30(m,1H),4.25-4.12(m,2H),3.94(m,2H),1.31(s,9H)；13C NMR(100MHz,CDCl3)δ149.0,141.0,125.9,111.7,82.85(d,J＝204.3Hz),59.75(d,J＝23.2Hz),33.9,31.5；HRMS(ESI)m/z C13H19NF[M+H]+:理论值208.1496,实测值208.1493。
实施例23
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔3-羟基氮杂环丁烷替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为79％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.44(dd,J＝8.0,4.6Hz,2H),6.44(dd,J＝8.0,4.6Hz,2H),4.89-4.72(m,1H),4.28-4.13(m,2H),3.81-3.71(m,2H)；13C NMR(100MHz,CDCl3)δ153.3,126.4(q,J＝3.4Hz),124.4(q,J＝270.2Hz),119.27(q,J＝32.2Hz),111.1,62.8,61.5；HRMS(ESI)m/z C10H11NOF3[M+H]+:理论值218.0787,实测值218.0790。
实施例24
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔氨基甲酸异丙酯替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为79％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.7Hz,2H),7.42(d,J＝8.7Hz,2H),6.66(s,1H),4.96(dt,J＝12.5,6.3Hz,1H),1.24(d,J＝6.3Hz,6H)；δ152.8,141.2,126.3(q,J＝3.8Hz),125.2(q,J＝64.3Hz).124.0(q,J＝239.8Hz),1178.0,69.3,22.0；HRMS(ESI)m/z C11H13NF3O2[M+H]+:理论值248.0893,实测值248.0896。
实施例25
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔3,5-二甲基吡唑替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为77％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.45(dd,J＝10.7,4.8Hz,2H),7.34(dd,J＝11.1,4.6Hz,2H),5.98(d,J＝6.5Hz,1H),2.30(d,J＝5.7Hz,6H),1.35(d,J＝7.1Hz,9H)；13C NMR(100MHz,CDCl3)δ150.5,148.8,139.5,137.5,126.0,124.5,106.7,34.7,31.5,13.7,12.5；HRMS(ESI)m/z C15H21N2[M+H]+:理论值229.1699,实测值229.1695。
实施例26
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔4-甲基苯胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为80％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.19(d,J＝7.7Hz,2H),6.98(d,J＝7.8Hz,2H),6.89(dd,J＝7.5,2.4Hz,4H),5.45(br,1H),2.21(s,3H),1.23(s,9H)；13CNMR(100MHz,CDCl3)δ143.6,141.3,141.0,130.4,129.9,126.2,118.3,117.3,34.2,31.6,20.8；HRMS(ESI)m/z C17H22N[M+H]+:理论值240.1747,实测值240.1750。
实施例27
本实施例中，用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，用等摩尔4-氧三氟甲基苯胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为79％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.38-7.22(m,3H),7.18-7.05(m,2H),7.04-6.96(m,3H),1.32(d,J＝2.8Hz,9H)；13C NMR(100MHz,CDCl3)δ145.1,142.9,139.9,126.4,124.8(t,J＝258.6Hz),122.4,119.3,118.9,117.5,34.4,31.6；19FNMR(376MHz,CDCl3)δ-58.33(s,OCF3).HRMS(ESI)m/zC17H19NF3O[M+H]+:理论值310.1413,实测值310.1417。
实施例28
本实施例中用等摩尔4-三氟甲基溴苯替换实施例1中的溴苯，2-萘胺替换实施例1中正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为81％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.70(dd,J＝16.4,8.3Hz,2H),7.54(d,J＝7.9Hz,2H),7.33-7.23(m,6H),7.03(d,J＝8.7Hz,1H),1.41(s,9H)；13C NMR(100MHz,CDCl3)δ150.4,141.3,134.1,130.6,128.7,128.1,128.0,126.4,126.2,124.6,122.2,120.1,118.2,34.8,31.6；HRMS(ESI)m/z C20H22N[M+H]+:理论值276.1747,实测值276.1743。

Claims (8)

1.一种光化学铁催化合成芳胺类化合物的方法，其特征在于：将式I所示芳基溴化物与式II所示胺类化合物、联吡啶、铁催化剂、有机碱加入有机溶剂中，在氩气氛围中加热并光照反应，反应完后分离纯化产物，得到式III所示芳胺类化合物；
式中，Ar代表芳基、取代芳基、杂环芳基、取代杂环芳基中任意一种，HNNu代表芳胺、取代芳胺、杂环芳胺、吡唑、酰胺、磺酰胺、脂肪胺中任意一种；
所述铁催化剂为溴化亚铁、碳酸亚铁、醋酸亚铁、氯化亚铁中任意一种；
所述有机碱为1,8-二氮杂二环十一碳-7-烯、四甲基胍、7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯、1,2-二甲基-1,4,5,6-四氢嘧啶中任意一种。
2.根据权利要求1所述的光化学铁催化合成芳胺类化合物的方法，其特征在于：所述Ar代表苯基、噻吩基、噻唑基、吡啶基、吡唑基、哌啶基、吡嗪基、喹啉基、苯丙噻吩基、苯并呋喃基、二苯并噻吩基、喹喔啉基中任意一种，或者含C1～C6烷基、C6～环烷基、叔丁基二甲基硅氧基、磺酰基、吖啶基、哌啶基、三甲基甲硅烷基、卤素、C1～C4烷氧基、三氟甲氧基、三氟甲基、氰基、酯基、醛基、酰基、羰基、硼酯基中至少1种取代基的苯基。
3.根据权利要求1或2所述的光化学铁催化合成芳胺类化合物的方法，其特征在于：所述胺类化合物的用量为芳基溴化物摩尔量的1.1～2倍。
4.根据权利要求1或2所述的光化学铁催化合成芳胺类化合物的方法，其特征在于：所述联吡啶的用量为芳基溴化物摩尔量的5％～15％。
5.根据权利要求1或2所述的光化学铁催化合成芳胺类化合物的方法，其特征在于：所述铁催化剂的用量为芳基溴化物摩尔量的5％～15％。
6.根据权利要求1或2所述的光化学铁催化合成芳胺类化合物的方法，其特征在于：所述有机碱的用量为芳基溴化物摩尔量的2～3倍。
7.根据权利要求1或2所述的光化学铁催化合成芳胺类化合物的方法，其特征在于：所述有机溶剂为二甲基亚砜、甲苯、异丙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中任意一种或两种。
8.根据权利要求1或2所述的光化学铁催化合成芳胺类化合物的方法，其特征在于：所述光照反应是在波长为360～430nm的紫外光照射下80～90℃反应24～36小时。
CN202311448033.8A 2023-11-02 2023-11-02 一种光化学铁催化合成芳胺类化合物的方法 Pending CN117466744A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311448033.8A CN117466744A (zh) 2023-11-02 2023-11-02 一种光化学铁催化合成芳胺类化合物的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311448033.8A CN117466744A (zh) 2023-11-02 2023-11-02 一种光化学铁催化合成芳胺类化合物的方法

Publications (1)

Publication Number Publication Date
CN117466744A true CN117466744A (zh) 2024-01-30

Family

ID=89637507

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311448033.8A Pending CN117466744A (zh) 2023-11-02 2023-11-02 一种光化学铁催化合成芳胺类化合物的方法

Country Status (1)

Country Link
CN (1) CN117466744A (zh)

Similar Documents

Publication Publication Date Title
Amal Joseph et al. Copper-mediated C–X functionalization of aryl halides
Das et al. Palladium-Catalyzed, ortho-Selective C–H Halogenation of Benzyl Nitriles, Aryl Weinreb Amides, and Anilides
Cepanec Synthesis of biaryls
Shi et al. Catalytic amination for N-alkyl amine synthesis
JP7199401B2 (ja) Ｎ－複素環カルベン及びその中間体の合成
JP6518242B2 (ja) ハロゲン化されたビフェニルアニリドおよびビフェニルアニリンの改善された製造方法
Feng et al. Pd-catalyzed decarboxylative cross-couplings of potassium malonate monoesters with aryl halides
CN109836457B (zh) 一种高位阻手性p,n,n配体及其制备方法和应用
CN117466744A (zh) 一种光化学铁催化合成芳胺类化合物的方法
JP2003183187A (ja) Ｎ−ヘテロ環式カルベン錯体およびその使用
CN101863826B (zh) 一种制备2-苄基吡啶类化合物的方法
CN108752213B (zh) 一种可见光激发二硫醚催化制备α-羟甲基-β-二羰基化合物的方法
Shang New Carbon–Carbon Coupling Reactions Based on Decarboxylation and Iron-Catalyzed C–H Activation
KR100424205B1 (ko) 방향족 요오드 화합물의 제조방법
CN109734548A (zh) 一种钯催化的芳基炔烃的制备方法
CA3059585A1 (en) Process for the preparation of deuterated ethanol from d2o
Fu Studies on Green Synthetic Reactions Based on Formic Acid from Biomass
Bobbitt Oxoammonium salt oxidations of alcohols
CN115141138B (zh) 一种烷基羧酸脱羧构建氟化物的方法
CN117466746A (zh) 一种光化学钴催化合成芳胺类化合物的方法
CN117466745A (zh) 一种光化学锰催化合成芳胺类化合物的方法
CN107629090B (zh) N,n-配位铑配合物、合成方法及其应用
CN114835541B (zh) 一种基于钯催化体系下手性四取代联烯酸类化合物的制备方法
CN116730879A (zh) 一种选择性合成4-氨基-n-（杂）芳基磺酰胺类化合物的方法
Danence Cooperativity in Catalysis: Co-Catalyst Assisted Palladium-Catalyzed Transformations

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination