铜催化选择性合成二芳胺和三芳胺的研究
|
摘要
二芳胺和三芳胺类化合物广泛应用于染料、药物和光电材料等领域中。铜催化的Ullmann反应是合成这类化合物的经典方法,然而它常常需要高温以及化学计量的铜试剂,适用的底物范围也很有限。近年来,温和条件下铜催化的C-N键的形成受到了广泛的关注。
本课题组在研究铜催化C-N偶联反应时发现邻氨基酚具有加速反应的性质：以Cu(Ⅰ)为催化剂碱性体系中,在不加入配体的情况下,邻氨基酚和碘苯即可在温和的条件下发生N-芳基化和N,N-二芳基化反应,生成含有邻位羟基的二芳胺和三芳胺产物。
本论文对影响邻氨基酚与卤代芳烃反应的铜盐、碱、溶剂、温度、原料摩尔比等因素进行研究,发现在以碘化亚铜为催化剂,磷酸钾或碳酸铯为碱,通过调节邻氨基酚与卤代芳烃的摩尔比和反应温度,可以选择性地得到邻氨基酚的N-芳基化和N,N-二芳基化产物。在N-芳基化反应的最佳的反应条件下,邻氨基酚及其衍生物的N-芳基化产物分离收率为63～92%。该反应具有广泛的官能团容忍性,可以容忍甲基,甲氧基,硝基,乙酰基甚至是游离的氨基和羟基。当对溴碘苯与邻氨基酚反应时,几乎专一性地生成2-(4-溴苯基氨基)苯酚,显示出该反应良好的化学选择性。在N,N-二芳基化反应的最佳条件下,反应得到了46-87%的邻羟基三芳胺类产物。底物范围的测试表明,该反应对甲基,甲氧基,乙酰基等有良好的容忍性；位阻效应对N,N-二芳基化反应的影响比较明显。
在邻氨基酚与硝基取代的卤代芳烃偶联反应中发现了邻氨基酚同时存在着N-芳基化和O-芳基化反应。通过在对温度、溶剂、反应时间等条件进行研究,成功控制了邻氨基酚的N-芳基化和O-芳基化的选择性,反应的收率分别为86%和74%。
苯酚、苯胺的混合物与对硝基氯苯的竞争性反应结果表明,N-芳基化是被邻氨基酚所导向的催化过程,O-芳基化是SNAr过程；碘苯与氨基酚类衍生物的偶联反应的结果表明,只有取代的氨基和羟基处于邻位才有明显的自催化效应。根据以上实验结果,推测了邻氨基酚自催化的反应机理：在碱的作用下邻氨基酚负离子与CuI形成稳定的五元环过渡态催化C-N键生成。
本文利用邻氨基酚的自催化效应,开发了一种直接、高效、选择性的合成带有邻羟基取代基的二芳胺和三芳胺类化合物的途径,并对硝基卤代芳烃为底物时N-芳基化和O-芳基反应进行了研究。
Di-and triarylamines are important building blocks in dyes, pharmaceuticals and photoelectric function materials. As one of the traditional methods to assemble these compounds, Ullmann reaction is limited by the harsh reaction condition, substrate scope and the moderate yield. Recently, much attention has been paid on Cu-catalyzed formation of C-N bonds.
In our previous work, we found o-aminophenol derivatives promoting Cu-catalyzed C-N bond formation. In further investigation, o-aminophenol could couple with iodobenzene in the Cu-catalyzed system without ligand which indicated their self-accelerating effect.
In this thesis, by investigating the effect facts in the reaction of o-aminophenol and aryl halides, such as copper, base, solvent and molar ratio of raw materials, we developed a ligand free system for selective N-arylation and N,N-diarylation. With the optimal reaction condition of N-arylation, o-aminophenol coupled with aryl halides to get diarylamines in 63-92%yields. The reaction also showed favorable functional group tolerance, such as methyl, methoxyl, acetyl, nitro, especially free hydroxyl and amine group. The different reactivity between iodides and bromides allowed us to obtain the 2-(4-bromophenyl-amino) phenol selectively. With the optimal reaction condition of N,N-diarylation, triarylamines could be obtain in the yield of 46-87%. Compared with N-arylation, the steric effect of N,N-diarylation was significant.
When o-aminophenol coupled with p-nitro aryl halides, N-arylation product and O-arylation product were obtained simultaneously. By investigating the reaction conditions, o-aminophenol could transforme to N-or Oarylation product selectively.
The results of further investigations indicated that self-accelerating effect occured in the condition of hydroxyl and amino group in ortho position.
Utilizing the dramatic self-accelerating effect of o-aminophenols, we developed a Cu-catalyzed system for the selective synthesizing di-and triarylamines. In addition, the N-and O-arylation products of o-aminophenol could be obtained when nitro aryl halides severed as substrates.
本课题组在研究铜催化C-N偶联反应时发现邻氨基酚具有加速反应的性质：以Cu(Ⅰ)为催化剂碱性体系中,在不加入配体的情况下,邻氨基酚和碘苯即可在温和的条件下发生N-芳基化和N,N-二芳基化反应,生成含有邻位羟基的二芳胺和三芳胺产物。
本论文对影响邻氨基酚与卤代芳烃反应的铜盐、碱、溶剂、温度、原料摩尔比等因素进行研究,发现在以碘化亚铜为催化剂,磷酸钾或碳酸铯为碱,通过调节邻氨基酚与卤代芳烃的摩尔比和反应温度,可以选择性地得到邻氨基酚的N-芳基化和N,N-二芳基化产物。在N-芳基化反应的最佳的反应条件下,邻氨基酚及其衍生物的N-芳基化产物分离收率为63～92%。该反应具有广泛的官能团容忍性,可以容忍甲基,甲氧基,硝基,乙酰基甚至是游离的氨基和羟基。当对溴碘苯与邻氨基酚反应时,几乎专一性地生成2-(4-溴苯基氨基)苯酚,显示出该反应良好的化学选择性。在N,N-二芳基化反应的最佳条件下,反应得到了46-87%的邻羟基三芳胺类产物。底物范围的测试表明,该反应对甲基,甲氧基,乙酰基等有良好的容忍性；位阻效应对N,N-二芳基化反应的影响比较明显。
在邻氨基酚与硝基取代的卤代芳烃偶联反应中发现了邻氨基酚同时存在着N-芳基化和O-芳基化反应。通过在对温度、溶剂、反应时间等条件进行研究,成功控制了邻氨基酚的N-芳基化和O-芳基化的选择性,反应的收率分别为86%和74%。
苯酚、苯胺的混合物与对硝基氯苯的竞争性反应结果表明,N-芳基化是被邻氨基酚所导向的催化过程,O-芳基化是SNAr过程；碘苯与氨基酚类衍生物的偶联反应的结果表明,只有取代的氨基和羟基处于邻位才有明显的自催化效应。根据以上实验结果,推测了邻氨基酚自催化的反应机理：在碱的作用下邻氨基酚负离子与CuI形成稳定的五元环过渡态催化C-N键生成。
本文利用邻氨基酚的自催化效应,开发了一种直接、高效、选择性的合成带有邻羟基取代基的二芳胺和三芳胺类化合物的途径,并对硝基卤代芳烃为底物时N-芳基化和O-芳基反应进行了研究。
Di-and triarylamines are important building blocks in dyes, pharmaceuticals and photoelectric function materials. As one of the traditional methods to assemble these compounds, Ullmann reaction is limited by the harsh reaction condition, substrate scope and the moderate yield. Recently, much attention has been paid on Cu-catalyzed formation of C-N bonds.
In our previous work, we found o-aminophenol derivatives promoting Cu-catalyzed C-N bond formation. In further investigation, o-aminophenol could couple with iodobenzene in the Cu-catalyzed system without ligand which indicated their self-accelerating effect.
In this thesis, by investigating the effect facts in the reaction of o-aminophenol and aryl halides, such as copper, base, solvent and molar ratio of raw materials, we developed a ligand free system for selective N-arylation and N,N-diarylation. With the optimal reaction condition of N-arylation, o-aminophenol coupled with aryl halides to get diarylamines in 63-92%yields. The reaction also showed favorable functional group tolerance, such as methyl, methoxyl, acetyl, nitro, especially free hydroxyl and amine group. The different reactivity between iodides and bromides allowed us to obtain the 2-(4-bromophenyl-amino) phenol selectively. With the optimal reaction condition of N,N-diarylation, triarylamines could be obtain in the yield of 46-87%. Compared with N-arylation, the steric effect of N,N-diarylation was significant.
When o-aminophenol coupled with p-nitro aryl halides, N-arylation product and O-arylation product were obtained simultaneously. By investigating the reaction conditions, o-aminophenol could transforme to N-or Oarylation product selectively.
The results of further investigations indicated that self-accelerating effect occured in the condition of hydroxyl and amino group in ortho position.
Utilizing the dramatic self-accelerating effect of o-aminophenols, we developed a Cu-catalyzed system for the selective synthesizing di-and triarylamines. In addition, the N-and O-arylation products of o-aminophenol could be obtained when nitro aryl halides severed as substrates.
引文
[1]Law K. Y. Organic photoconductive materials:recent trends and developments [J]. Chemical Reviews,1993,93 (1):449-486.
[2]Shirota Y., Kageyama H. Charge carrier transporting molecular materials and their applications in devices [J]. Chemical Reviews,2007,107, (4):953-1010.
[3]薛金强,王世荣,李祥高.二芳胺类化合物的合成及其在光电功能材料中的应用[J].化学工业与工程,2005,22(2)：120-125.
[4]Matsuki Y., Dan J., Fukuhara, K., et al. Isolation and Characterization of Human Urinary Metabolites of Meclomen [J]. Chemical& Pharmaceutical Bulletin,1988, 36, (4):1431-1436.,
[5]Hartwig J. F. Transition metal catalyzed synthesis of arylamines and aryl ethers from aryl halides and triflates:Scope and mechanism [J]. Angewandte Chemie-International Edition,1998,37, (15):2047-2067.
[6]Hartwig J. F. Carbon-heteroatom bond-forming reductive eliminations of amines, ethers, and sulfides [J]. Accounts of Chemical Research,1998,31, (12):852-860.
[7]Ley S. V., Thomas A. W. Modern synthetic methods for copper-mediated C(aryl)-0, C(aryl)-N, and C(aryl)-S bond formation [J]. Angewandte Chemie-International Edition,2003,42, (44):5400-5449.
[8]Corbet J. P., Mignani G. Selected patented cross-coupling reaction technologies [J]. Chemical Reviews,2006,106, (7):2651-2710.
[9]Monnier F., Taillefer M. Catalytic C-C, C-N, and C-0 Ullmann-Type Coupling Reactions [J]. Angewandte Chemie International Edition,2009,48, (38):6954-6971.
[10]PlanteO. J., BuchwaldS. L., Seeberger P. H. Halobenzyl ethers as protecting groups for organic synthesis [J]. Journal of the American Chemical Society,2000,122, (29):7148-7149.
[11]Harris, M. C.; Huang, X. H.; Buchwald, S. L., Improved functional group compatibility in the palladium-catalyzed synthesis of aryl amines [J]. Organic Letters,2002,4, (17):2885-2888.
[12]Harris M. C., Huang X. H., Buchwald, S. L. Improved functional group compatibility in the palladium-catalyzed synthesis of aryl amines [J]. Organic Letters,2002, 4, (17):2885-2888.
[13]ShenQ. L., Hartwig J. F. [(CyPF-Bu-t)PdC12]:An air-stable, one-component, highly efficient catalyst for amination of heteroaryl and aryl halides [J]. Organic Letters,2008,10, (18):4109-4112.
[14]ShenQ., Ogata T., Hartwig J. F. Highly reactive, general and long-lived catalysts for palladium-catalyzed amination of heteroaryl and aryl chlorides, bromides, and iodides:Scope and structure-activity relationships [J]. Journal of the American Chemical Society,2008,130, (20):6586-6596.
[15]Ullmann F. A new path for preparing diphenylamine derivatives [J].Chem. Be,1903, 36:2382.
[16]薛敏钊,黄得音,刘燕刚.三苯胺衍生物的制备方法[P].中国,1322710A.2001.
[17]唐培堃.精细有机合成化学及工艺学[M].天津大学出版社,1993.
[18]越山博喜.二芳胺制备方法[P].JP 6 100 504,1994-04-12.
[19]Szabo P., Islington, Freeman D.E., et al. Preparation of unsymmetrical diphenylamines [P].US:4485260,1984-11-27.
[20]Manufacture of Diayrlamines:US250819[P].1926.
[21]Kosugi M., Kameyama M., Migita T. Palladium-Catalyzed Aromatic Amination of Aryl Bromides with N,N-Diethylamino-Tributyltin [J]. Chemistry Letters,1983, (6): 927-928.
[22]Guram A. S., Rennels R. A., Buchwald S. L. A Simple Catalytic Method for the Conversion of Aryl Bromides to Arylamines [J]. Angewandte Chemie-International Edition in English,1995, 34, (12):1348-1350.
[23]Louie J., Hartwig J. F. Palladium-Catalyzed Synthesis of Arylamines from Aryl Halides-Mechanistic Studies Lead to Coupling in the Absence of Tin Reagents [J]. Tetrahedron Letters,1995,36, (21):3609-3612.
[24]Driver M. S., Hartwig J. F. A second-generation catalyst for aryl halide amination: Mixed secondary amines from aryl halides and primary amines catalyzed by (DPPF)PdC12 [J]. Journal of the American Chemical Society,1996,118, (30): 7217-7218.
[25]Wolfe J. P., Wagaw S.; Buchwald S. L. An improved catalyst system for aromatic carbon-nitrogen bond formation:The possible involvement of bis(phosphine) palladium complexes as key intermediates [J]. Journal of the American Chemical Society,1996,118, (30),7215-7216.
[26]Hartwig J. F., Kawatsura M., Hauck S. I., et al. Room-temperature palladium-catalyzed amination of aryl bromides and chlorides and extended scope of aromatic C-N bond formation with a commercial ligand [J]. Journal of Organic Chemistry, 1999,64 (15):5575-5580.
[27]Kuwano R., Utsunomiya M., Hartwig J. F. Aqueous hydroxide as a base for palladium-catalyzed amination of aryl chlorides and bromides [J]. Journal of Organic Chemistry,2002,67 (18):6479-6486.
[28]Surendra Harkal F. R., Alexander Zapf, Christa Fuhrmann, Thomas Riermeier, Axel Monsees, Matthias Beller. Dialkylphosphinoimidazoles as new ligands for palladium-catalyzed coupling reactions of aryl chlorides [J]. Advanced Synthesis & Catalysis,2004,346 (13-15):1742-1748.
[29]Gajare A. S., Toyota K., Yoshifuji M., et al. Solvent free amination reactions of aryl bromides at room temperature catalyzed by a (pi-allyl) palladium complex bearing a diphosphinidenecyclobutene ligand [J]. Journal of Organic Chemistry, 2004,69 (19):6504-6506.
[30]Bhanushali M. J., Nandurkar N. S., Bhor M. D., et al. Palladium/1,2-bis. (diphenylphosphino) ethane catalysed amination of aryl halides with aliphatic/aromatic amines [J]. Journal of Molecular Catalysis (A)-Chemical,2006, 259 (1-2):46-50.
[31]Surry D. S., Buchwald S. L. Selective palladium-catalyzed arylation of ammonia: Synthesis of anilines as well as symmetrical and unsymmetrical Di-and triarylamines [J]. Journal of the American Chemical Society,2007,129 (34): 10354-10355.
[32]ShenQ. L., HartwigJ. F. [(CyPF-Bu-t) PdCl2]:An air-stable, one-component, highly efficient catalyst for amination of heteroaryl and aryl halides [J]. Organic Letters,2008,10 (18):4109-4112.
[33]Chen G. S., Lam W. H., Fok W. S., et al. Easily accessible benzamide-derived P,0 ligands (Bphos) for palladium-catalyzed carbon-nitrogen bond-forming reactions [J]. Chemistry-an Asian Journal,2007,2 (2):306-313.
[34]Maiti D., Buchwald S. L. Orthogonal Cu-and Pd-Based Catalyst Systems for the 0-and N-Arylation of Aminophenols [J]. Journal of the American Chemical Society, 2009,131, (47):17423-17429.
[35]Reviews:(a) Hartwig J. F. In handbook of organopalladium chemistry for organic synthesis [M]. Negishi E., Ed.;. Wiley-Interscience:New York,2002:1051; (b) Yang B. H., Buchwald S. L. Palladium-catalyzed amination of aryl halides and sulfonates [J]. Journal of Organometalic Chemistry,1999,576 (1-2):125-146; (c) Zapf A. Beller M. The development of efficient catalysts for palladium-catalyzed coupling reactions of aryl halides [J]. Chemical Communications,2005, (4):431-440. (d)Surry D. S., Buchwald S. L. Biaryl phosphane ligands in palladium-catalyzed amination [J]. Angewandte Chemie-International Edition,2008,47, (34): 6338-6361.
[36]Wolfe J. P., Buchwald S. L. Nickel-catalyzed amination of aryl chlorides [J]. Journal of the American Chemical Society,1997,119, (26):6054-6058.
[37]Lipshutz B. H., Ueda H. Aromatic Aminations by Heterogeneous Ni(0)/C Catalysis [J]. Angewandte Chemie-International Edition,2000,39, (24):4492-4494.
[38]Desmarets C., Schneider R., Fort Y. Nickel (0)/dihydroimidazol-2-ylidene complex catalyzed coupling of aryl chlorides and amines [J]. Journal of Organic Chemistry, 2002,67 (9):3029-3036.
[39]Chen C., Yang L. M. Arylation of diarylamines catalyzed by Ni (Ⅱ)-PPh3 system [J]. Organic Letters,2005,7, (11):2209-2211.
[40]Chen C., Yang L. M. Ni(Ⅱ)-(σ-Aryl) complex:A facile, efficient catalyst for nickel-catalyzed carbon-nitrogen coupling reactions [J]. Journal of Organic Chemistry,2007,72 (16):6324-6327.
[41]Gao C. Y., Cao X. B., Yang L. M. Nickel-catalyzed cross-coupling of diarylamines with haloarenes [J]. Organic& Biomolecular Chemistry,2009,7, (19):3922-3925.
[42]Hartwig J. F. Carbon-heteroatom bond-forming reductive eliminations of amines, ethers, and sulfides [J]. Accounts of Chemical Research,1998,31, (12),852-860.
[43]Marcoux J. F., Buchwald S. L. A General Copper-Catalyzed Synthesis of Diary l Ethers [J] Journal of the American Chemical Society,1997,119, (26):10539-10540.
[44]Kiyomori A., Marcoux J. F., Buchwald S. L. An Efficient Copper-Catalyzed Coupling of Aryl Halides with Imidazoles [J]. Tetrahedron Lett,1999,40 (14):2657-2660.
[45]Goodbrand H. B., HuN. X. Ligand-accelerated catalysis of the Ullmann condensation: Application to hole conducting triarylamines [J]. Journal of Organic Chemistry, 1999,64 (2):670-674.
[46]Gujadhur R., Venkataraman D., Kintigh J. T. Formation of aryl-nitrogen bonds using a soluble copper (I) catalyst [J]. Tetrahedron Letters,2001,42 (29):4791-4793.
[47]Gujadhur R. K., Venkataraman D. Formation of aryl-nitrogen, aryl-oxygen, and aryl-carbon bonds using well-defined copper (I)-based catalysts [J]. Organic Letters,2001,3 (26):4315-4317.
[48]Kelkar A. A., Patil N. M., Chaudhari R. V. Copper-catalyzed amination of aryl halides:single-step synthesis of triarylamines [J]. Tetrahedron Letters,2002, 43 (40):7143-7146.
[49]Gajare A. S., Toyota K., Yoshifuji M., et al. Application of a diphosphinidenecyclobutene ligand in the solvent-free copper-catalysed amination reactions of aryl halides [J]. Chemical Communications,2004, (17):1994-1995.
[50]Haider J., Kunz K., Scholz U. Highly selective copper-catalyzed monoarylation of aniline [J]. Advanced Synthesis & Catalysis,2004,346 (7):717-722.
[51]Ma Dawei, Zhang Yongda, Yao Jiangchao, et al. Accelerating effect induced by the structure of α-amino acid in the copper-catalyzed coupling reaction of aryl halides with α-amino acids:Synthesis of benzolactam-V8 [J]. Journal of the American Chemical Society,1998,120 (48):12459-12467.
[52]Zhang H., Cai Q., Ma D. W. Amino acid promoted CuI-catalyzed ON bond formation between aryl halides and amines or N-containing heterocycles [J]. Journal of Organic Chemistry,2005,70 (13):5164-5173.
[53]Rao H. H., Fu H., Jiang Y. Y., et al. Copper-catalyzed arylation of amines using diphenyl pyrrolidine-2-phosphonate as the new ligand [J]. Journal of Organic Chemistry,2005,70 (20):8107-8109.
[54]Rao H. H., Jin Y., Fu H., et al. A versatile and efficient ligand for copper-catalyzed formation of C-N,C-0, and P-C bonds:Pyrrolidine-2-phosphonic acid phenyl monoester [J]. Chemistry-A European Journal,2006,12 (13):3636-3646.
[55]Guo X., Rao H. H., Fu H., et al. An inexpensive and efficient copper catalyst for N-arylation of amines, Amides and nitrogen-containing heterocycles [J]. Advanced Synthesis& Catalysis,2006,348 (15):2197-2202.
[56]Liu Y. H., Chen C., Yang L. M. Diazabutadiene:a simple and efficient ligand for copper-catalyzed N-arylation of aromatic amines [J]. Tetrahedron Letters,2006, 47 (52):9275-9278.
[57]Rout L., Jammi S., Punniyamurthy T. Novel CuO nanoparticle catalyzed C-N cross coupling of amines with iodobenzene [J]. Organic Letters,2007,9 (17):3397-3399.
[58]Yifeng Liu, Juan Zhang, Yangyang Li, et al. Optimization of the conditions for copper-mediated N-Arylation of heteroarylamines [J]. European Journal of Organic Chemistry,2007, (36):6084-6088.
[59]Nandurkar N. S., Bhanushali M. J., Bhor M. D., et al. N-Arylation of aliphatic, aromatic and heteroaromatic amines catalyzed by copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate) [J]. Tetrahedron Letters,2007,48 (37): 6573-6576.
[60]Altman R. A., Anderson K. W., Buchwald S. L. Pyrrole-2-carboxylic acid as a ligand for the Cu-catalyzed reactions of primary anilines with aryl halides [J]. Journal of Organic Chemistry,2008,73 (13):5167-5169.
[61]Xu H. H., Wolf C. Copper catalyzed coupling of aryl chlorides, bromides and iodides with amines and amides [J]. Chemical Communications 2009, (13):1715-1717.
[62]张强,宋东明,曹煜东.邻氨基酚合成中氧化副产物2-氨基吩嗪-3-酮的研究[J].染料工业,1998,35(1)：25-27.
[2]Shirota Y., Kageyama H. Charge carrier transporting molecular materials and their applications in devices [J]. Chemical Reviews,2007,107, (4):953-1010.
[3]薛金强,王世荣,李祥高.二芳胺类化合物的合成及其在光电功能材料中的应用[J].化学工业与工程,2005,22(2)：120-125.
[4]Matsuki Y., Dan J., Fukuhara, K., et al. Isolation and Characterization of Human Urinary Metabolites of Meclomen [J]. Chemical& Pharmaceutical Bulletin,1988, 36, (4):1431-1436.,
[5]Hartwig J. F. Transition metal catalyzed synthesis of arylamines and aryl ethers from aryl halides and triflates:Scope and mechanism [J]. Angewandte Chemie-International Edition,1998,37, (15):2047-2067.
[6]Hartwig J. F. Carbon-heteroatom bond-forming reductive eliminations of amines, ethers, and sulfides [J]. Accounts of Chemical Research,1998,31, (12):852-860.
[7]Ley S. V., Thomas A. W. Modern synthetic methods for copper-mediated C(aryl)-0, C(aryl)-N, and C(aryl)-S bond formation [J]. Angewandte Chemie-International Edition,2003,42, (44):5400-5449.
[8]Corbet J. P., Mignani G. Selected patented cross-coupling reaction technologies [J]. Chemical Reviews,2006,106, (7):2651-2710.
[9]Monnier F., Taillefer M. Catalytic C-C, C-N, and C-0 Ullmann-Type Coupling Reactions [J]. Angewandte Chemie International Edition,2009,48, (38):6954-6971.
[10]PlanteO. J., BuchwaldS. L., Seeberger P. H. Halobenzyl ethers as protecting groups for organic synthesis [J]. Journal of the American Chemical Society,2000,122, (29):7148-7149.
[11]Harris, M. C.; Huang, X. H.; Buchwald, S. L., Improved functional group compatibility in the palladium-catalyzed synthesis of aryl amines [J]. Organic Letters,2002,4, (17):2885-2888.
[12]Harris M. C., Huang X. H., Buchwald, S. L. Improved functional group compatibility in the palladium-catalyzed synthesis of aryl amines [J]. Organic Letters,2002, 4, (17):2885-2888.
[13]ShenQ. L., Hartwig J. F. [(CyPF-Bu-t)PdC12]:An air-stable, one-component, highly efficient catalyst for amination of heteroaryl and aryl halides [J]. Organic Letters,2008,10, (18):4109-4112.
[14]ShenQ., Ogata T., Hartwig J. F. Highly reactive, general and long-lived catalysts for palladium-catalyzed amination of heteroaryl and aryl chlorides, bromides, and iodides:Scope and structure-activity relationships [J]. Journal of the American Chemical Society,2008,130, (20):6586-6596.
[15]Ullmann F. A new path for preparing diphenylamine derivatives [J].Chem. Be,1903, 36:2382.
[16]薛敏钊,黄得音,刘燕刚.三苯胺衍生物的制备方法[P].中国,1322710A.2001.
[17]唐培堃.精细有机合成化学及工艺学[M].天津大学出版社,1993.
[18]越山博喜.二芳胺制备方法[P].JP 6 100 504,1994-04-12.
[19]Szabo P., Islington, Freeman D.E., et al. Preparation of unsymmetrical diphenylamines [P].US:4485260,1984-11-27.
[20]Manufacture of Diayrlamines:US250819[P].1926.
[21]Kosugi M., Kameyama M., Migita T. Palladium-Catalyzed Aromatic Amination of Aryl Bromides with N,N-Diethylamino-Tributyltin [J]. Chemistry Letters,1983, (6): 927-928.
[22]Guram A. S., Rennels R. A., Buchwald S. L. A Simple Catalytic Method for the Conversion of Aryl Bromides to Arylamines [J]. Angewandte Chemie-International Edition in English,1995, 34, (12):1348-1350.
[23]Louie J., Hartwig J. F. Palladium-Catalyzed Synthesis of Arylamines from Aryl Halides-Mechanistic Studies Lead to Coupling in the Absence of Tin Reagents [J]. Tetrahedron Letters,1995,36, (21):3609-3612.
[24]Driver M. S., Hartwig J. F. A second-generation catalyst for aryl halide amination: Mixed secondary amines from aryl halides and primary amines catalyzed by (DPPF)PdC12 [J]. Journal of the American Chemical Society,1996,118, (30): 7217-7218.
[25]Wolfe J. P., Wagaw S.; Buchwald S. L. An improved catalyst system for aromatic carbon-nitrogen bond formation:The possible involvement of bis(phosphine) palladium complexes as key intermediates [J]. Journal of the American Chemical Society,1996,118, (30),7215-7216.
[26]Hartwig J. F., Kawatsura M., Hauck S. I., et al. Room-temperature palladium-catalyzed amination of aryl bromides and chlorides and extended scope of aromatic C-N bond formation with a commercial ligand [J]. Journal of Organic Chemistry, 1999,64 (15):5575-5580.
[27]Kuwano R., Utsunomiya M., Hartwig J. F. Aqueous hydroxide as a base for palladium-catalyzed amination of aryl chlorides and bromides [J]. Journal of Organic Chemistry,2002,67 (18):6479-6486.
[28]Surendra Harkal F. R., Alexander Zapf, Christa Fuhrmann, Thomas Riermeier, Axel Monsees, Matthias Beller. Dialkylphosphinoimidazoles as new ligands for palladium-catalyzed coupling reactions of aryl chlorides [J]. Advanced Synthesis & Catalysis,2004,346 (13-15):1742-1748.
[29]Gajare A. S., Toyota K., Yoshifuji M., et al. Solvent free amination reactions of aryl bromides at room temperature catalyzed by a (pi-allyl) palladium complex bearing a diphosphinidenecyclobutene ligand [J]. Journal of Organic Chemistry, 2004,69 (19):6504-6506.
[30]Bhanushali M. J., Nandurkar N. S., Bhor M. D., et al. Palladium/1,2-bis. (diphenylphosphino) ethane catalysed amination of aryl halides with aliphatic/aromatic amines [J]. Journal of Molecular Catalysis (A)-Chemical,2006, 259 (1-2):46-50.
[31]Surry D. S., Buchwald S. L. Selective palladium-catalyzed arylation of ammonia: Synthesis of anilines as well as symmetrical and unsymmetrical Di-and triarylamines [J]. Journal of the American Chemical Society,2007,129 (34): 10354-10355.
[32]ShenQ. L., HartwigJ. F. [(CyPF-Bu-t) PdCl2]:An air-stable, one-component, highly efficient catalyst for amination of heteroaryl and aryl halides [J]. Organic Letters,2008,10 (18):4109-4112.
[33]Chen G. S., Lam W. H., Fok W. S., et al. Easily accessible benzamide-derived P,0 ligands (Bphos) for palladium-catalyzed carbon-nitrogen bond-forming reactions [J]. Chemistry-an Asian Journal,2007,2 (2):306-313.
[34]Maiti D., Buchwald S. L. Orthogonal Cu-and Pd-Based Catalyst Systems for the 0-and N-Arylation of Aminophenols [J]. Journal of the American Chemical Society, 2009,131, (47):17423-17429.
[35]Reviews:(a) Hartwig J. F. In handbook of organopalladium chemistry for organic synthesis [M]. Negishi E., Ed.;. Wiley-Interscience:New York,2002:1051; (b) Yang B. H., Buchwald S. L. Palladium-catalyzed amination of aryl halides and sulfonates [J]. Journal of Organometalic Chemistry,1999,576 (1-2):125-146; (c) Zapf A. Beller M. The development of efficient catalysts for palladium-catalyzed coupling reactions of aryl halides [J]. Chemical Communications,2005, (4):431-440. (d)Surry D. S., Buchwald S. L. Biaryl phosphane ligands in palladium-catalyzed amination [J]. Angewandte Chemie-International Edition,2008,47, (34): 6338-6361.
[36]Wolfe J. P., Buchwald S. L. Nickel-catalyzed amination of aryl chlorides [J]. Journal of the American Chemical Society,1997,119, (26):6054-6058.
[37]Lipshutz B. H., Ueda H. Aromatic Aminations by Heterogeneous Ni(0)/C Catalysis [J]. Angewandte Chemie-International Edition,2000,39, (24):4492-4494.
[38]Desmarets C., Schneider R., Fort Y. Nickel (0)/dihydroimidazol-2-ylidene complex catalyzed coupling of aryl chlorides and amines [J]. Journal of Organic Chemistry, 2002,67 (9):3029-3036.
[39]Chen C., Yang L. M. Arylation of diarylamines catalyzed by Ni (Ⅱ)-PPh3 system [J]. Organic Letters,2005,7, (11):2209-2211.
[40]Chen C., Yang L. M. Ni(Ⅱ)-(σ-Aryl) complex:A facile, efficient catalyst for nickel-catalyzed carbon-nitrogen coupling reactions [J]. Journal of Organic Chemistry,2007,72 (16):6324-6327.
[41]Gao C. Y., Cao X. B., Yang L. M. Nickel-catalyzed cross-coupling of diarylamines with haloarenes [J]. Organic& Biomolecular Chemistry,2009,7, (19):3922-3925.
[42]Hartwig J. F. Carbon-heteroatom bond-forming reductive eliminations of amines, ethers, and sulfides [J]. Accounts of Chemical Research,1998,31, (12),852-860.
[43]Marcoux J. F., Buchwald S. L. A General Copper-Catalyzed Synthesis of Diary l Ethers [J] Journal of the American Chemical Society,1997,119, (26):10539-10540.
[44]Kiyomori A., Marcoux J. F., Buchwald S. L. An Efficient Copper-Catalyzed Coupling of Aryl Halides with Imidazoles [J]. Tetrahedron Lett,1999,40 (14):2657-2660.
[45]Goodbrand H. B., HuN. X. Ligand-accelerated catalysis of the Ullmann condensation: Application to hole conducting triarylamines [J]. Journal of Organic Chemistry, 1999,64 (2):670-674.
[46]Gujadhur R., Venkataraman D., Kintigh J. T. Formation of aryl-nitrogen bonds using a soluble copper (I) catalyst [J]. Tetrahedron Letters,2001,42 (29):4791-4793.
[47]Gujadhur R. K., Venkataraman D. Formation of aryl-nitrogen, aryl-oxygen, and aryl-carbon bonds using well-defined copper (I)-based catalysts [J]. Organic Letters,2001,3 (26):4315-4317.
[48]Kelkar A. A., Patil N. M., Chaudhari R. V. Copper-catalyzed amination of aryl halides:single-step synthesis of triarylamines [J]. Tetrahedron Letters,2002, 43 (40):7143-7146.
[49]Gajare A. S., Toyota K., Yoshifuji M., et al. Application of a diphosphinidenecyclobutene ligand in the solvent-free copper-catalysed amination reactions of aryl halides [J]. Chemical Communications,2004, (17):1994-1995.
[50]Haider J., Kunz K., Scholz U. Highly selective copper-catalyzed monoarylation of aniline [J]. Advanced Synthesis & Catalysis,2004,346 (7):717-722.
[51]Ma Dawei, Zhang Yongda, Yao Jiangchao, et al. Accelerating effect induced by the structure of α-amino acid in the copper-catalyzed coupling reaction of aryl halides with α-amino acids:Synthesis of benzolactam-V8 [J]. Journal of the American Chemical Society,1998,120 (48):12459-12467.
[52]Zhang H., Cai Q., Ma D. W. Amino acid promoted CuI-catalyzed ON bond formation between aryl halides and amines or N-containing heterocycles [J]. Journal of Organic Chemistry,2005,70 (13):5164-5173.
[53]Rao H. H., Fu H., Jiang Y. Y., et al. Copper-catalyzed arylation of amines using diphenyl pyrrolidine-2-phosphonate as the new ligand [J]. Journal of Organic Chemistry,2005,70 (20):8107-8109.
[54]Rao H. H., Jin Y., Fu H., et al. A versatile and efficient ligand for copper-catalyzed formation of C-N,C-0, and P-C bonds:Pyrrolidine-2-phosphonic acid phenyl monoester [J]. Chemistry-A European Journal,2006,12 (13):3636-3646.
[55]Guo X., Rao H. H., Fu H., et al. An inexpensive and efficient copper catalyst for N-arylation of amines, Amides and nitrogen-containing heterocycles [J]. Advanced Synthesis& Catalysis,2006,348 (15):2197-2202.
[56]Liu Y. H., Chen C., Yang L. M. Diazabutadiene:a simple and efficient ligand for copper-catalyzed N-arylation of aromatic amines [J]. Tetrahedron Letters,2006, 47 (52):9275-9278.
[57]Rout L., Jammi S., Punniyamurthy T. Novel CuO nanoparticle catalyzed C-N cross coupling of amines with iodobenzene [J]. Organic Letters,2007,9 (17):3397-3399.
[58]Yifeng Liu, Juan Zhang, Yangyang Li, et al. Optimization of the conditions for copper-mediated N-Arylation of heteroarylamines [J]. European Journal of Organic Chemistry,2007, (36):6084-6088.
[59]Nandurkar N. S., Bhanushali M. J., Bhor M. D., et al. N-Arylation of aliphatic, aromatic and heteroaromatic amines catalyzed by copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate) [J]. Tetrahedron Letters,2007,48 (37): 6573-6576.
[60]Altman R. A., Anderson K. W., Buchwald S. L. Pyrrole-2-carboxylic acid as a ligand for the Cu-catalyzed reactions of primary anilines with aryl halides [J]. Journal of Organic Chemistry,2008,73 (13):5167-5169.
[61]Xu H. H., Wolf C. Copper catalyzed coupling of aryl chlorides, bromides and iodides with amines and amides [J]. Chemical Communications 2009, (13):1715-1717.
[62]张强,宋东明,曹煜东.邻氨基酚合成中氧化副产物2-氨基吩嗪-3-酮的研究[J].染料工业,1998,35(1)：25-27.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |