查看“︁乌尔曼二芳醚合成”︁的源代码

{{另见|乌尔曼反应}}

'''乌尔曼二芳醚合成'''，又称'''乌尔曼缩合反应'''、'''乌尔曼联苯醚合成'''、'''乌尔曼型反应'''，指[[酚]]与[[芳基]][[卤化物]]在[[铜]]或铜盐催化下[[偶联]]为[[二芳醚]]。<ref>{{cite journal en
 | title = Ueber die Phenylirung von Phenolen  
 | author = [[Fritz Ullmann]], Paul Sponagel  
 | journal =  [[Berichte der deutschen chemischen Gesellschaft]]
 | volume = 38
 | issue = 2
 | pages = 2211–2212 
 | year = 1905 
 | url =  
 | doi = 10.1002/cber.190503802176   }}</ref> 例如，[[对硝基苯酚]]与[[溴苯]]在铜存在下偶联为对硝基[[联苯醚]]。<ref>Ray Q. Brewster and Theodore Groening, "[http://www.orgsyn.org/orgsyn/prep.asp?prep=cv2p0445 Ether, ''p''-nitrophenyl phenyl] {{Wayback|url=http://www.orgsyn.org/orgsyn/prep.asp?prep=cv2p0445 |date=20121019165316 }}", ''[[Organic Syntheses]]'', Coll. Vol. 2, p.445.</ref>

[[File:UllmannCondensation.svg|center|乌尔曼二芳醚合成]]

这个反应是[[乌尔曼反应]]的变体，也是以德国化学家弗里茨·乌尔曼的名字命名。

[[苯胺]]与芳基[[酰胺]]代替酚进行的类似反应称为[[戈尔德贝格反应]]。<ref>{{cite journal en
 | title = Ueber Phenylirungen bei Gegenwart von Kupfer als Katalysator
 | author = Iram Goldberg  
 | journal = [[Berichte der deutschen chemischen Gesellschaft]] 
 | volume = 39 
 | issue = 2
 | pages = 1691–1692 
 | year = 1906 
 | url =  
 | doi = 10.1002/cber.19060390298}}</ref>

反应常在高沸点溶剂（如[[N-甲基吡咯烷酮|''N''-甲基吡咯烷酮]]、[[硝基苯]]、[[二甲基甲酰胺]]）中、高温下（一般超过210°C）和计量的铜存在下进行。反应中需要用到的活性铜粉可通过用[[锌]]还原热的[[硫酸铜]]水溶液来制备。芳卤底物芳环上的[[吸电子基]]或邻位[[羧基]]使反应更容易进行。<ref>{{cite journal en|title=Minireview Catalytic CC, CN, and CO Ullmann-Type Coupling Reactions|author=Florian Monnier, Marc Taillefer|journal=[[Angewandte Chemie International Edition]]|volume=48|issue=38|pages=6954–6971|year=2009|doi=10.1002/anie.200804497}}</ref>

最近发现了在碱和二胺配体存在下，用催化量的[[碘化铜]]介导的乌尔曼二芳醚合成，重新引发了对这个反应的研究兴趣。<ref>{{cite journal en|title=Copper-Catalyzed Formation of Carbon-Heteroatom and Carbon-Carbon Bonds|author=Buchwald, Stephen L. ''et al.''|year=2003|volume=2003 WO02/085838|url=http://www.wipo.int/pctdb/en/fetch.jsp?SEARCH_IA=US2002012785&DBSELECT=PCT&C=00&TOTAL=1&IDB=0&TYPE_FIELD=256&SERVER_TYPE=19-00&SORT=41275182-SCORE&QUERY=WO02%2F085838&START=1&ELEMENT_SET=BASICHTML-ENG&RESULT=1&DISP=25&FORM=SEP-0%2FHITNUM%2CB-ENG%2CDP%2CMC%2CPA%2CABSUM-ENG%2C%2CSCORE&IDOC=1288017&IA=US2002012785&LANG=ENG&DISPLAY=DESC}}{{dead link|date=2017年11月 |bot=InternetArchiveBot |fix-attempted=yes }}</ref><ref>{{cite journal en|title=Copper in cross-coupling reactions: The post-Ullmann chemistry |author=Irina P. Beletskaya|journal=Coordination Chemistry Reviews|year=2004|volume=248|issue=21-24|pages=2337–2364|doi=10.1016/j.ccr.2004.09.014 }}</ref> 

==反应机理==
:<math>\rm \ Cu\!-\!X + Ar\!-\!OH \ +</math>　碱　<math>\rm \ \rightarrow Cu\!-\!O\!-\!Ar + HX \ + </math>　碱
:<math>\rm \ Cu\!-\!O\!-\!Ar + Ar'\!-\!X \rightarrow Ar\!-\!O\!-\!Cu(\!-\!Ar)\!-\!X</math> （[[氧化加成]]）
:<math>\rm \ Ar\!-\!O\!-\!Cu(\!-\!Ar)\!-\!X \rightarrow Ar\!-\!O\!-\!Ar' + Cu\!-\!X</math> （[[还原消除]]）

==戈尔德贝格反应==
'''戈尔德贝格反应'''（Goldberg reaction）是用[[苯胺]]或[[芳基]][[酰胺]]<ref>{{cite journal en
 | title = A General and Efficient Copper Catalyst for the Amidation of Aryl Halides and the N-Arylation of Nitrogen Heterocycles 
 | author = Klapars, A.; Antilla, J. C.; Huang, X.; Buchwald, S. L.  
 | journal = [[J. Am. Chem. Soc.]]（Communication） 
 | volume = 123 
 | issue = 31
 | pages = 7727–7729  
 | year = 2001 
 | url =
 | doi = 10.1021/ja016226z   }}</ref><ref>{{cite journal en
 | title = A General and Efficient Copper Catalyst for the Amidation of Aryl Halides 
 | author = Klapars, A.; Huang, X.; Buchwald, S. L.  
 | journal = J. Am. Chem. Soc.（Article） 
 | volume = 124 
 | issue = 25
 | pages = 7421–7428 
 | year = 2002 
 | url =
 | doi = 10.1021/ja0260465   }}</ref><ref>{{cite journal en
 | title = The Role of Chelating Diamine Ligands in the Goldberg Reaction: A Kinetic Study on the Copper-Catalyzed Amidation of Aryl Iodides 
 | author = Strieter, E. R.; Blackmond, D. G.; Buchwald, S. L.  
 | journal =  [[J. Am. Chem. Soc.]]（Communication） 
 | volume = 127 
 | issue = 12
 | pages = 4120–4121 
 | year = 2005 
 | url =
 | doi = 10.1021/ja050120c}}</ref>代替[[酚]]进行的乌尔曼二芳醚合成。由德国女化学家、弗里茨·乌尔曼的妻子伊尔玛·戈尔德贝格<ref>{{cite journal en
 | title = Ueber Phenylirungen bei Gegenwart von Kupfer als Katalysator
 | author = Iram Goldberg  
 | journal = [[Berichte der deutschen chemischen Gesellschaft]] 
 | volume = 39 
 | issue = 2
 | pages = 1691–1692 
 | year = 1906 
 | url =
 | doi = 10.1002/cber.19060390298}}</ref>发现。

例如，[[邻氯苯甲酸]]与[[苯胺]]缩合，可得[[芬那酸]]。<ref>{{OrgSynth | title = Acridone | author = C. F. H. Allen and G. H. W. McKee | collvol = 2 | collvolpages = 15 | prep = cv2p0015 | year = 1943}}</ref>

[[File:GoldbergReaction.svg|center|利用戈尔德贝格反应合成芬那酸]]

邻溴苯乙酮与苯甲酰胺进行偶联的产物，可以用作[[Camps环化反应]]的起始原料。<ref>{{cite journal en
 | title = Sequential Cu-Catalyzed Amidation-Base-Mediated Camps Cyclization: A Two-Step Synthesis of 2-Aryl-4-quinolones from o-Halophenones 
 | author =  Jones, C. P.; Anderson, K. W.; Buchwald, S. L. 
 | journal = [[J. Org. Chem.]] 
 | volume = 72
 | issue = 21
 | pages = 7968–7973 
 | year = 2007  
 | url =
 | doi = 10.1021/jo701384n   }}</ref>

[[File:BuchwaldAmidationReaction.svg|600px|center|Buchwald酰胺化反应]]

戈尔德贝格等报道了一种用从[[碘化亚铜]]和[[邻二氮菲]]制备的催化剂介导的芳基碘化物和芳胺之间的乌尔曼型芳香胺化偶联反应。富电子的芳基碘化物也能进行反应，因此这种方法可用于弥补[[布赫瓦尔德-哈特维希反应]]有些情况下不适用于富电子芳卤的缺点。<ref>{{cite journal en
 | title = Ligand-Accelerated Catalysis of the Ullmann Condensation: Application to Hole Conducting Triarylamines 
 | author = H.B. Goodbrand, Nan-Xing Hu  
 | journal = [[Journal of Organic Chemistry]]
 | volume = 64 
 | issue =
 | pages = 670–674 
 | year = 1999 
 | url =
 | doi = 10.1021/jo981804o   }}</ref>

==Hurtley反应==
'''Hurtley反应'''（Hurtley reaction）是[[芳香族化合物|芳]][[卤代烃|卤]]与[[氢碳酸]]在[[碱]]和[[铜]]或铜盐存在下进行[[偶联]]。<ref>{{cite journal en|title=CCXLIV.—Replacement of halogen in orthobromo-benzoic acid|author=William Robert Hardy Hurtley|journal=[[J. Chem. Soc.]]|year=1929|pages=1870–1873|doi=10.1039/JR9290001870}}</ref>

[[File:HurtleyReaction.svg|center|Hurtley反应]]

这个反应是乌尔曼二芳醚合成的一种变体。原始文献是用[[邻溴苯甲酸]]与[[丙二酸酯]]（和其他二羰基化合物）在[[乙醇钠]]存在下进行偶联。

==参见==
*[[化学反应列表]]

==参考资料==
{{Reflist}}

[[Category:碳-杂原子键形成反应]]
[[Category:缩合反应]]
[[Category:人名反应]]