CN108774122B - 一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮类化合物的方法 - Google Patents

一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮类化合物的方法 Download PDF

Info

Publication number
CN108774122B
CN108774122B CN201810910070.9A CN201810910070A CN108774122B CN 108774122 B CN108774122 B CN 108774122B CN 201810910070 A CN201810910070 A CN 201810910070A CN 108774122 B CN108774122 B CN 108774122B
Authority
CN
China
Prior art keywords
chloroform
acid
transition metal
compound
iodide
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.)
Active
Application number
CN201810910070.9A
Other languages
English (en)
Other versions
CN108774122A (zh
Inventor
韩维
徐方宁
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.)
Nanjing Normal University
Original Assignee
Nanjing 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 Nanjing Normal University filed Critical Nanjing Normal University
Priority to CN201810910070.9A priority Critical patent/CN108774122B/zh
Publication of CN108774122A publication Critical patent/CN108774122A/zh
Application granted granted Critical
Publication of CN108774122B publication Critical patent/CN108774122B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
    • C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/45—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/24—Sulfones; Sulfoxides having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/788—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with keto groups bound to a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/792—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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 with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/333—Radicals substituted by oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • 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
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
    • 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/643—2-Phenoxypyridines; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole 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
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
    • C07D277/24—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/192—Radicals derived from carboxylic acids from aromatic carboxylic acids
    • 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
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/80—Radicals substituted by oxygen 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
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—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
    • C07D409/06—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 only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮类化合物的方法。本发明在溶剂醇或醇的水溶液中，在碱、酸和碘化物的作用下，无需过渡金属参与，芳基卤代物、芳硼类化合物与氯仿为羰基源进行交叉偶联反应来制备二芳甲酮类化合物。本发明的交叉偶联反应制备二芳甲酮类化合物的方法，最显著的优势为不使用过渡金属催化剂和氯仿为羰基源；具有无需过渡金属催化剂带来的成本低和没有金属残留的优势；羰基源安全、廉价和易于处理；反应条件温和且选择性高；底物来源广泛且稳定；底物官能团相容性好且底物的适用范围广，在优化的反应条件之下，目标产品分离收率高达95％。

Description

一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮 类化合物的方法
技术领域
本发明属于催化合成技术领域，更具体地说，涉及一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮类化合物的方法，是一种无过渡金属参与的直接利用芳基卤代物、芳硼类化合物与氯仿为羰基源进行交叉偶联反应来制备二芳甲酮类化合物的方法。
背景技术
羰基化的Suzuki反应具有反应选择性好、产率高、底物来源广泛和稳定性好、底物适用范围广和官能团相容性好的优点，能用于合成高附加值的二芳甲酮类化合物，因此引起了广泛的关注。目前，催化羰基化的Suzuki反应的催化体系一般都要用到昂贵的钯催化剂和膦配体，然而膦配体有毒、对空气和水不稳定，且价格昂贵。虽然稳定的氮卡宾配体和氮配体也用于此反应，但是配体的引入给反应的后处理造成困难，而且也增加了生产成本。此外，钯在产品的残留，通常难以除去，特别是在制药工业对金属残留的控制十分严格。显而易见，发展无需过渡金属催化剂和配体参与的羰基化Suzuki反应来合成二芳甲酮类化合物具有重要的应用价值。
羰基化的Suzuki反应一般需要较大一氧化碳的压力下才能顺利进行，限制了该反应的广泛应用(X.-F.Wu,M.Beller,Transition Metal Catalyzed CarbonylationReactions-Carbonylative Activation of C–X Bonds,Springer-Verlag Berlin,Heidelberg,2013)。而且，一氧化碳有毒、易燃和难于处理，存在严重的安全问题。因此，开发更加安全和有效的羰基源具有重要的研究意义和应用价值。
发明内容
发明目的：针对现有的羰基化合成二芳甲酮的方法存在通常需要昂贵的过渡金属催化剂以及使用过渡金属产生的金属残留等不足和羰基源有毒、易燃、难于处理，存在严重的安全隐患等问题，本发明提供一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮类化合物的方法，在无过渡金属催化剂作用下，芳卤类化合物、芳基硼类化合物与氯仿羰基源进行直接偶联合成二芳甲酮，该方法具有无需过渡金属催化剂带来的成本低和没有金属残留的优势；羰基源安全、廉价和易于处理；反应条件温和且选择性高；底物来源广泛且稳定；底物官能团相容性好且底物的适用范围广。
技术方案：为了实现上述目的，如本发明所述一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮类化合物的方法，包括如下步骤：
无需过渡金属催化剂，将芳基卤代物、芳硼类化合物与氯仿为羰基源进行交叉偶联反应，合成二芳甲酮类化合物，反应通式表示如下：
Figure BDA0001761634760000021
式中：X＝I，Br或Cl；Ar-X表示芳基或杂芳基的卤代物；Ar’-B表示芳基或杂芳基的硼酸、硼酸酯或氟硼酸盐。
作为优选，所述偶联反应温度为50～200℃，反应时间为0.5～72小时。
其中，Ar-X中的芳基为苯基、联苯基、萘基、蒽基、菲基或芘基，Ar-X中的杂芳基为含N、O或S的五至十三元环的杂芳基；Ar’-B中的芳基为苯基、联苯基、萘基、蒽基、菲基或芘基，Ar’-B中的杂芳基为含N、O或S的五至十三元环的杂芳基。
其中，Ar-X或Ar’-B中的杂芳基为呋喃基、噻吩基、吡咯基、吲哚基、咔唑基、吡唑基、噻唑基、恶唑基、咪唑基或吡啶基。
其中，所述Ar上的取代基以R表示，R单取代或多取代芳环上的氢；Ar’上的取代基以R’表示，R’单取代或多取代芳环上的氢；其中
R任意选自氢，C1～C12的烷基、烯基或炔基，C1～C12的烷氧基，C1～C12的卤取代烷基，C3～C12的环烷基，芳基、芳氧基或芳胺基，杂芳基、杂芳氧基或杂芳胺基，C1～C12烷基取代的氨基，C1～C12的巯基，氟、氯或溴，羟基，C1～C12烷基羰基，羧基，C1～C12烷氧基羰基，C1～C12烷胺基羰基，芳基羰基，C1～C12烷磺酰基、磺酸基、氰基或硝基；
R’任意选自氢，C1～C12烷基、烯基或炔基，C1～C12烷氧基、C1～C12的卤取代烷基、C3～C12的环烷基，芳基、芳氧基或芳胺基，杂芳基、杂芳氧基或杂芳胺基，C1～C12烷基取代的氨基，C1～C12的巯基，氟、氯或溴，羟基，C1～C12烷基羰基，羧基，C1～C12烷氧基羰基，C1～C12烷胺基羰基，芳基羰基，C1～C12烷磺酰基，磺酸基，氰基或硝基。
其中，所述Ar或Ar’表示杂芳基吡咯基、吲哚基、咔唑基、吡唑基和咪唑基时，其氮原子上的取代基任意选自氢、C1～C12的烷基、C1～C12卤取代烷基、C3～C12的环烷基、芳基、杂芳基、C1～C12烷磺酰基、対甲苯磺酰基、苄基、C1～C12烷基羰基、叔丁氧酰基或芳酰基。
进一步地，所述偶联反应以醇或醇的水溶液为溶剂，在碱、酸和碘化物的作用下进行。
进一步地，所述醇为乙醇，异丙醇，正丁醇，叔丁醇，乙二醇，甘油，葡萄糖或平均分子量为100～10000的聚乙二醇；醇的水溶液中醇与水的体积比为1:(0～1000)。
进一步地，所述的碱为磷酸钾、磷酸氢钾、磷酸氢二钾、磷酸钠、磷酸氢钠、磷酸氢二钠、氟化钠、氟化钾、氟化铯、碳酸锂、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铯、醋酸钠、醋酸钾、醋酸铯、特戊酸钠、特戊酸钾、特戊酸铯、甲醇钠、乙醇钠，乙醇钾、叔丁醇锂、叔丁醇钠、叔丁醇钾、氢氧化锂、氢氧化钠、氢氧化钾、氢氧化铯、四丁基氟化铵、四丁基氢氧化铵、三乙胺、二异丙基乙胺或吡啶中的一种或几种；
所述酸为甲酸、乙酸、丙酸、异丙酸、特戊酸、三氟乙酸、苯甲酸、2-硝基苯甲酸、三氟甲磺酸、对甲苯磺酸或樟脑磺酸；
所述的碘化物为碘化氢、碘化锂、碘化钠、碘化钾、碘化铵、四甲基碘化铵、四乙基碘化铵、四丙基碘化铵、四丁基碘化铵、四正庚基碘化铵、三甲基碘化锍、三甲基碘化亚砜、甲基三苯基碘化鏻或乙基三苯基碘化鏻。
作为优选，所述的芳基卤代物、芳硼类化合物、羰基源、碱、酸、碘化物的摩尔比为1:(0.5～10):(1～20):(1～50):(0.01～20):(0.01～20)；所述的芳基卤代物与溶剂的重量比为1:(5～1000)。
本发明的方法所合成的二芳甲酮类化合物的结构通式为：
Figure BDA0001761634760000031
有益效果：相比于现有技术，本发明的有益效果为：
(1)本发明提供了一种在醇或醇的水溶液中无需过渡金属催化剂的芳基卤代物、芳硼类化合物与氯仿为羰基源进行直接交叉偶联反应来制备二芳甲酮化合物的新方法，该方法具有无需过渡金属催化剂的显著优势，避免了使用过渡金属催化剂导致的反应成本增加、后处理困难以及过渡金属残留的问题。
(2)本发明提供了一种在醇或醇的水溶液中无需过渡金属催化剂的芳基卤代物、芳硼类化合物与氯仿为羰基源进行直接交叉偶联反应来制备二芳甲酮化合物的新方法，该方法使用氯仿为羰基源，具有来源广泛、稳定和易于处理的优势，避免了使用常规的一氧化碳为羰基源存在的易燃、有毒和难以处理的问题。
(3)本发明提供的二芳甲酮类化合物的合成方法简单易行，一步法直接得到二芳甲酮类化合物，在优化的反应条件之下，目标产品分离后收率可高达95％，是一种高效、经济、安全和环境友好的合成二芳甲酮的方法。
(4)本发明方法制备的二芳甲酮可用来制备具有独特的生物、药理活性和功能的杂环化合物，在药物中间体、生物活性分子和荧光材料等方面有着广泛的用途。
具体实施方式
下面结合具体实施例对本发明进一步进行说明。
实施例1
化合物1：25mL反应瓶中依次加入4-氟苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，4-碘苯乙炔(0.5mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率86％。
实施例2
化合物1：25mL反应瓶中依次加入4-氟苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，4-碘苯乙炔(0.5mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在50℃下反应72h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率25％。
实施例3
化合物1：25mL反应瓶中依次加入4-氟苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，4-碘苯乙炔(0.5mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在200℃下反应0.5h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率90％。
实施例4
化合物2：25mL反应瓶中依次加入2-甲基苯硼酸(0.75mmol)，叔丁醇钠(1.0mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，4-环丙基碘苯(0.5mmol)，氯仿(1.5mmol)和聚乙二醇-1000(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率88％。
实施例5
化合物2：25mL反应瓶中依次加入2-甲基苯硼酸(10mmol)，碳酸钠(12.5mmol)，一水合氢氧化铯(37.5mmol)，碘化钠(10mmol)，特戊酸(10mmol)，4-环丙基碘苯(0.5mmol)，氯仿(10mmol)和乙二醇(122g)，并在120℃下反应2h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率86％。
实施例6
化合物2：25mL反应瓶中依次加入2-甲基苯硼酸(0.25mmol)，碳酸钠(0.125mmol)，一水合氢氧化铯(0.375mmol)，碘化钠(0.005mmol)，特戊酸(0.005mmol)，4-环丙基碘苯(0.5mmol)，氯仿(0.5mmol)和乙二醇(0.65g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率35％。
实施例7
化合物2：25mL反应瓶中依次加入2-甲基苯硼酸(2.5mmol)，碳酸钠(5.0mmol)，一水合氢氧化铯(20.0mmol)，碘化钠(5.0mmol)，特戊酸(5.0mmol)，4-环丙基碘苯(0.5mmol)，氯仿(5.0mmol)和乙二醇(61g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率95％。
实施例8
化合物3：25mL反应瓶中依次加入4-硝基碘苯(0.5mmol)，4-环己基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应5h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率66％。
实施例9
化合物3：25mL反应瓶中依次加入4-硝基碘苯(0.5mmol)，4-环己基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)，乙二醇(1.5g)和水(0.5g)，并在120℃下反应12h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率62％。
实施例10
化合物3：25mL反应瓶中依次加入4-硝基碘苯(0.5mmol)，4-环己基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)，异丙醇(2g)，并在120℃下反应12h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率55％。
实施例11
化合物3：25mL反应瓶中依次加入4-硝基碘苯(0.5mmol)，4-环己基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)，甘油(2g)，并在120℃下反应12h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率60％。
实施例12
化合物4：25mL反应瓶中依次加入4-苯氧基碘苯(0.5mmol)，3-乙氧基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率92％。
实施例13
化合物5：25mL反应瓶中依次加入2-氟-4-丁酰基苯硼酸(0.75mmol)，氟化钠(1.0mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，1-碘萘(0.5mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应48h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率90％。
实施例14
化合物5：25mL反应瓶中依次加入2-氟-4-丁酰基苯硼酸(0.5mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.0mmol)，碘化钠(0.05mmol)，1-碘萘(0.5mmol)，特戊酸(0.05mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应48h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率65％。
实施例15
化合物6：25mL反应瓶中依次加入4-N,N-二乙基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，9-碘蒽(0.5mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应48h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率87％。
实施例16
化合物7：25mL反应瓶中依次加入4-吡咯烷酰基苯硼酸嚬呐醇酯(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，4-碘联苯(0.5mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应48h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率85％。
实施例17
化合物8：25mL反应瓶中依次加入3-苯氧基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，4-碘苯乙烯(0.5mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和聚乙二醇-400(2.0g)，并在120℃下反应12h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率80％。
实施例18
化合物8：25mL反应瓶中依次加入3-苯氧基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，4-碘苯乙烯(0.5mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)，聚乙二醇-400(1.8g)和水(0.2g)，并在120℃下反应12h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率79％。
实施例19
化合物9：25mL反应瓶中依次加入3-氟-5-乙巯基苯硼酸(0.75mmol)，磷酸氢二钾(1.5mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，3,5-二甲基碘苯(0.5mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率92％。
实施例20
化合物9：25mL反应瓶中依次加入3-氟-5-乙巯基苯硼酸(0.75mmol)，磷酸氢二钾(1.5mmol)，碳酸钠(0.65mmol)，一水合氢氧化铯(1.2mmol)，碘化钠(0.25mmol)，3,5-二甲基碘苯(0.5mmol)，特戊酸(0.75mmol)，氯仿(0.55mmol)和乙二醇(2.0g)，并在120℃下反应48h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率67％。
实施例21
化合物10：25mL反应瓶中依次加入2-碘吡啶(0.5mmol)，3-全氟乙基基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和聚乙二醇-1000(2.0g)，并在120℃下反应48h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率82％。
实施例22
化合物10：25mL反应瓶中依次加入2-碘吡啶(0.5mmol)，3-全氟乙基基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)，聚乙二醇-10000(0.5g)和水(1.5g)，并在120℃下反应48h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率61％。
实施例23
化合物11：25mL反应瓶中依次加入4-乙氧酰基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，4-碘噻吩(0.5mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应48h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率80％。
实施例24
化合物12：25mL反应瓶中依次加入2-氯苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，四丁基氢氧化铵(2.5mmol)，碘化钠(0.25mmol)，4-氯碘苯(0.5mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率86％。
实施例25
化合物12：25mL反应瓶中依次加入2-氯苯硼酸(3.0mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(12mmol)，碘化钠(2.0mmol)，4-氯碘苯(0.5mmol)，特戊酸(5.0mmol)，氯仿(5mmol)和乙二醇(5.0g)和水(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率95％。
实施例26
化合物13：25mL反应瓶中依次加入4-(2’-吡啶氧基)碘苯(0.5mmol)，4-氰基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率89％。
实施例27
化合物14：25mL反应瓶中依次加入4-碘苯酚(0.5mmol)，3-乙磺酰基苯硼酸(0.75mmol)，二异丙基乙胺(1.0mmol),碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率80％。
实施例28
化合物15：25mL反应瓶中依次加入4-碘苯甲酸(0.5mmol)，2-甲基苯硼酸(0.75mmol)，醋酸钾(1.5mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率80％。
实施例29
化合物16：25mL反应瓶中依次加入4-(2-炔丙氧基)碘苯(0.5mmol)，1-丙基吲哚-7-硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，乙基三苯基碘化鏻(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和甘油(2.0g)，并在120℃下反应48h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率78％。
实施例30
化合物17：25mL反应瓶中依次加入苯并呋喃-3-硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，2-碘呋喃(0.5mmol)，特戊酸(0.75mmol)，碘仿(1.5mmol)和聚乙二醇-400(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率87％。
实施例31
化合物18：25mL反应瓶中依次加入1-甲基-2-碘吡咯(0.5mmol)，1-萘氟硼酸钾(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率85％。
实施例32
化合物19：25mL反应瓶中依次加入4-三氟甲基苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，四丁基碘化铵(0.25mmol)，2-碘恶唑(0.5mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和聚乙二醇-400(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率91％。
实施例33
化合物20：25mL反应瓶中依次加入4-联苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，五氟碘苯(0.5mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应48h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率65％。
实施例34
化合物21：25mL反应瓶中依次加入1-苄吲哚-3-硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，2-碘噻唑(0.5mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率87％。
实施例35
化合物22：25mL反应瓶中依次加入1-苯基-2-碘咪唑(0.5mmol)，1-乙酰基吲哚-3-硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和聚乙二醇-200(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率82％。
实施例36
化合物23：25mL反应瓶中依次加入4-碘二苯甲酮(0.5mmol)，1-对甲苯磺酰基吲哚-3-硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率84％。
实施例37
化合物24：25mL反应瓶中依次加入1-叔丁氧羰基-4-碘吡唑(0.5mmol)，1-环丙基吲哚-3-硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率85％。
实施例38
化合物25：25mL反应瓶中依次加入1-苯甲酰基吲哚-3-硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，3-乙巯基碘苯(0.5mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)和乙二醇(2.0g)，并在120℃下反应48h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率81％。
实施例39
化合物26：25mL反应瓶中依次加入1-乙磺酰基-4-碘咔唑(0.5mmol)，3-噻吩苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)，聚乙二醇-8000(2.0g)和水(10g)，并在120℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率83％。
实施例40
化合物26：25mL反应瓶中依次加入1-乙磺酰基-4-碘咔唑(0.5mmol)，3-噻吩苯硼酸(0.75mmol)，碳酸钠(1.0mmol)，一水合氢氧化铯(2.5mmol)，碘化钠(0.25mmol)，特戊酸(0.75mmol)，氯仿(1.5mmol)，异丙醇(2.0g)和水(0.1g)，并在80℃下反应24h。冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到产率52％。
实施例1～40二芳甲酮的合成方法对应的实验结果列于表1：
表1无过渡金属参与的二芳甲酮的合成反应[a]
Figure BDA0001761634760000111
Figure BDA0001761634760000121
Figure BDA0001761634760000131
Figure BDA0001761634760000141
[a]反应条件见实施例；[b]柱分离收率。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，酸在本发明中起减少非羰基化的副反应之作用，利用的是其酸性，理论上给出的各种酸，都应能取得类似之效果；碱是发生芳卤代物羰基化偶联反应所必须的促进剂，利用的是其碱性，理论上给出的各种碱，都应能取得类似之效果；碘化物是羰基化化反应常见的促进剂，利用的是碘阴离子的作用，理论上能电离出碘阴离子的碘化物，都应能取得类似之效果；芳基卤代物发生反应的化学键是碳-卤键，而其芳环上的取代基影响的是芳环的电子云密度大小以及反应时的空间位阻大小，即取代基的修饰只是一定程度上影响反应，不对反应的发生起决定作用；芳硼试剂发生反应的化学键是碳-硼键，而其芳环上的取代基影响的是芳环的电子云密度大小以及反应时的空间位阻大小，即取代基的修饰只是一定程度上影响反应，不对反应的发生起决定作用。任何熟悉本专业的技术人员不难理解，在不脱离本发明技术方案范围内，当可进行替换、变动或修饰得到相应的实施例，例如对于所述的取代基可在本发明范围内进行替换、改变或修饰，均可以实现本发明方法。但凡是未脱离本发明技术方案的宗旨，依据本发明的对以上实施例所作的任何修改、修饰或等同与等效的变化，均仍属于本发明技术方案的范围内。

Claims (1)

1.一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮类化合物的方法，其特征在于，包括如下步骤：
无需过渡金属催化剂，将芳基卤代物、芳硼类化合物与氯仿为羰基源进行交叉偶联反应，合成二芳甲酮类化合物，反应通式表示如下：
Figure FDA0003022111080000011
式中：Ar-X为4-氯碘苯0.5mmol，Ar’-B为2-氯苯硼酸3.0mmol；
所述交叉偶联反应以醇或醇的水溶液为溶剂，在碱、酸和碘化物的作用下进行，包括碳酸钠1.0mmol，一水合氢氧化铯12mmol，碘化钠2.0mmol，特戊酸5.0mmol，氯仿5mmol和乙二醇5.0g和水2.0g，在120℃下反应24h，冷却到室温，萃取，减压蒸除溶剂后柱层析分离得到
Figure FDA0003022111080000012
CN201810910070.9A 2018-08-10 2018-08-10 一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮类化合物的方法 Active CN108774122B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810910070.9A CN108774122B (zh) 2018-08-10 2018-08-10 一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮类化合物的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810910070.9A CN108774122B (zh) 2018-08-10 2018-08-10 一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮类化合物的方法

Publications (2)

Publication Number Publication Date
CN108774122A CN108774122A (zh) 2018-11-09
CN108774122B true CN108774122B (zh) 2021-06-11

Family

ID=64029193

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810910070.9A Active CN108774122B (zh) 2018-08-10 2018-08-10 一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮类化合物的方法

Country Status (1)

Country Link
CN (1) CN108774122B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113861002B (zh) * 2021-11-02 2024-04-26 琼台师范学院 一种无金属催化体系催化氧化芳香醇类制备芳香酮类化合物的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104892335A (zh) * 2015-05-14 2015-09-09 南京师范大学 一种常压下无金属催化合成二芳甲酮的方法
CN106116999A (zh) * 2016-06-21 2016-11-16 南京师范大学 一种铁催化羰基化合成二芳甲酮的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104892335A (zh) * 2015-05-14 2015-09-09 南京师范大学 一种常压下无金属催化合成二芳甲酮的方法
CN106116999A (zh) * 2016-06-21 2016-11-16 南京师范大学 一种铁催化羰基化合成二芳甲酮的方法

Also Published As

Publication number Publication date
CN108774122A (zh) 2018-11-09

Similar Documents

Publication Publication Date Title
Guo et al. Silver tungstate: a single-component bifunctional catalyst for carboxylation of terminal alkynes with CO 2 in ambient conditions
Chen et al. Homocoupling reaction of terminal alkynes catalyzed by a reusable cationic 2, 2′-bipyridyl palladium (II)/CuI system in water
Miyaura et al. A new stereospecific cross-coupling by the palladium-catalyzed reaction of 1-alkenylboranes with 1-alkenyl or 1-alkynyl halides
Thorpe et al. Regio-and stereoselective copper-catalyzed β-borylation of allenoates by a preactivated diboron
Blakemore suzuki–miyaura coupling
Mondal et al. Eco-friendly Suzuki–Miyaura coupling of arylboronic acids to aromatic ketones catalyzed by the oxime-palladacycle in biosolvent 2-MeTHF
Xu et al. Palladium‐Catalyzed Intramolecular Aminofluorination of Styrenes
Widdowson et al. Palladium catalysed Suzuki reactions of fluoroarenes
Gooßen Pd-catalyzed synthesis of arylacetic acid derivatives from boronic acidsDedicated to Professor KB Sharpless on the occasion of his 60th birthday.
Shen et al. Bidentate auxiliary-directed alkenyl C–H allylation via exo-palladacycles: synthesis of branched 1, 4-dienes
Tsukamoto et al. Palladium (0)-catalyzed direct cross-coupling reaction of allyl alcohols with aryl-and vinyl-boronic acids
Zhang et al. N-Heterocyclic carbene-palladium (II)-1-methylimidazole complex catalyzed allyl-aryl coupling of allylic alcohols with arylboronic acids in neat water
CN107840819B (zh) 一种多取代异吲哚啉酮衍生物的合成方法
Wang et al. N-Heterocyclic carbene–palladium (ii)–1-methylimidazole complex-catalyzed Suzuki–Miyaura coupling of benzyl carbamates with arylboronic acids
CN108774122B (zh) 一种无过渡金属参与的氯仿为羰基源的羰基化合成二芳甲酮类化合物的方法
Zhou et al. Atom‐Efficient, Palladium‐Catalyzed Stille Coupling Reactions of Tetraphenylstannane with Aryl Iodides or Aryl Bromides in Polyethylene Glycol 400 (PEG‐400)
Pan et al. Copper (II)‐Catalyzed Tandem Synthesis of Substituted 3‐Methyleneisoindolin‐1‐ones
Hansen et al. Direct synthesis of 1, 1-diarylalkenes from alkenyl phosphates via nickel (0)-catalysed Suzuki–Miyaura coupling
CN108558635B (zh) 3-芳基丙炔酸类及3-芳基丙炔酸酯类化合物的制备方法
US20030149273A1 (en) Complexes of N-heterocyclic carbenes and the use thereof
Huang et al. Copper (I)‐Catalyzed Intramolecular Direct C‐Arylation of Azoles with Aryl Bromides
Li et al. Ytterbium (III) triflate-catalyzed asymmetric nucleophilic addition of functionalized lithium (α-carbalkoxyvinyl) cuprates to chiral p-toluenesulfinimines (thiooxime S-oxides)
CN111057080B (zh) 一种含硼吲哚啉酮衍生物的制备方法
Dilauro et al. Cobalt-catalyzed cross-coupling reactions of aryl-and alkylaluminum derivatives with (hetero) aryl and alkyl bromides
JP2003300940A (ja) ビアリール化合物の製造法

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
GR01 Patent grant
GR01 Patent grant