N-苯基哌啶的气相催化合成
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摘要
N-苯基哌啶作为一种重要的有机原料和精细化工产品,在工业、农业和医药等领域中应用非常广泛。由苯胺和1,5-戊二醇气相合成N-苯基哌啶是N-苯基哌啶众多合成方法中最为经济的一种。与传统的合成方法相比较,该方法简便、成本低廉,并且避免了使用传统液相法中所需的大量有毒有机溶剂。本论文报道了一种简易可行的以γ-Al2O3作为催化剂的气相催化合成N-苯基哌啶的方法,通过常压气固相反应及NH3-TPD、BET和TG等表征方法对该催化剂进行了深入研究。主要得到了如下实验结果:
1.以直接升温焙烧方法制备用于苯胺和1,5-戊二醇气相合成N-苯基哌啶的γ-Al2O3催化剂。该催化剂不仅制备方法简便、易于重复,而且活性和选择性较高。
2.当活性Al2O3由室温升温至500℃并在此温度下焙烧4 h,在300℃的反应温度下N-苯基哌啶的收率可以达到92%。
3.向反应体系通入氢气可以很好地清除催化剂表面的积碳。
4.具有一定比表面积和孔容的γ-Al2O3催化剂活性高、选择性好。孔容过大或过小都不利于N-苯基哌啶的生成。
5.通过量子化学计算和实验对苯胺和1,5-戊二醇合成N-苯基哌啶的反应机理进行了探讨,推出在γ-Al2O3催化剂的存在下,该反应是1,5-戊二醇先脱水生成四氢吡喃,然后四氢吡喃再和苯胺反应生成产物N-苯基哌啶。
N-phenylpiperidine, which is an important organic raw material and fine chemical product, has many uses in the fields of industry, agriculture and medicine. There are many methods to produce N-phenylpiperidine. However, from the industrial, environmental and economical points of view, the synthesis from aniline and 1,5-pentanediol seems to be one of the most promising routes. Because it is easy from the reactants to N-phenylpiperidine and the raw materials are inexpensive, a low cost process on the industrial scale could be possible. Moreover, this method avoids using a large amount of organic solvent. Herein, we report a simple and practical catalyzed procedure for the synthesis of N-phenylpiperidine overγ-Al2O3 catalyst. The catalyst was investigated by means of some characterizations such as NH3-TPD, BET and TG . The main results are summarized as follows:
1.γ-Al2O3 catalyst prepared by temperature-direct-calcination, exhibited very high activity and selectivity for the reaction of aniline and 1,5-pentanediol. It was prepared easily as well as obtained repeatly.
2. When the active alumina was calcined at 500℃for 4 h with temperature-direct calcination method, the yield of N-phenylpiperidine could be up to 92% at the reaction temperature of 300℃.
3. The carbon-deposition could be efficiently suppressed when hydrogen was added to the reaction system.
4.γ-Al2O3 catalyst with appropriate specific surface area and total pore volume has high catalytic activity and selectivity. Too big or too small total pore volume couldn’t favor to obtain the high yield of N-phenylpiperidine.
5. The mechanism of the reaction from aniline and 1,5-pentanediol to N-phenylpiperidine was investigated by quantum chemistry calculation. The dehydration of 1,5-pentanediol to tetrahydropyran is first presumed, then the synthesis of N-phenylpiperidine from tetrahydropyran and aniline takes place.
1.以直接升温焙烧方法制备用于苯胺和1,5-戊二醇气相合成N-苯基哌啶的γ-Al2O3催化剂。该催化剂不仅制备方法简便、易于重复,而且活性和选择性较高。
2.当活性Al2O3由室温升温至500℃并在此温度下焙烧4 h,在300℃的反应温度下N-苯基哌啶的收率可以达到92%。
3.向反应体系通入氢气可以很好地清除催化剂表面的积碳。
4.具有一定比表面积和孔容的γ-Al2O3催化剂活性高、选择性好。孔容过大或过小都不利于N-苯基哌啶的生成。
5.通过量子化学计算和实验对苯胺和1,5-戊二醇合成N-苯基哌啶的反应机理进行了探讨,推出在γ-Al2O3催化剂的存在下,该反应是1,5-戊二醇先脱水生成四氢吡喃,然后四氢吡喃再和苯胺反应生成产物N-苯基哌啶。
N-phenylpiperidine, which is an important organic raw material and fine chemical product, has many uses in the fields of industry, agriculture and medicine. There are many methods to produce N-phenylpiperidine. However, from the industrial, environmental and economical points of view, the synthesis from aniline and 1,5-pentanediol seems to be one of the most promising routes. Because it is easy from the reactants to N-phenylpiperidine and the raw materials are inexpensive, a low cost process on the industrial scale could be possible. Moreover, this method avoids using a large amount of organic solvent. Herein, we report a simple and practical catalyzed procedure for the synthesis of N-phenylpiperidine overγ-Al2O3 catalyst. The catalyst was investigated by means of some characterizations such as NH3-TPD, BET and TG . The main results are summarized as follows:
1.γ-Al2O3 catalyst prepared by temperature-direct-calcination, exhibited very high activity and selectivity for the reaction of aniline and 1,5-pentanediol. It was prepared easily as well as obtained repeatly.
2. When the active alumina was calcined at 500℃for 4 h with temperature-direct calcination method, the yield of N-phenylpiperidine could be up to 92% at the reaction temperature of 300℃.
3. The carbon-deposition could be efficiently suppressed when hydrogen was added to the reaction system.
4.γ-Al2O3 catalyst with appropriate specific surface area and total pore volume has high catalytic activity and selectivity. Too big or too small total pore volume couldn’t favor to obtain the high yield of N-phenylpiperidine.
5. The mechanism of the reaction from aniline and 1,5-pentanediol to N-phenylpiperidine was investigated by quantum chemistry calculation. The dehydration of 1,5-pentanediol to tetrahydropyran is first presumed, then the synthesis of N-phenylpiperidine from tetrahydropyran and aniline takes place.
引文
[1]王大全主编,精细化工词典,化学工业出版社,1998,1
[2]石雷,由苯胺和乙二醇一步催化合成吲哚的研究:[博士学位论文].大连:大连理工大学,2002,
[3]殷福珊,陈银广,刘学民等,脂肪醇的胺化反应,日用化学工业,1996年第4期
[4]唐靖,陈骏如,李瑞祥等,芳胺常压气相N-烷基化反应研究,化学研究与应用(Chemical Research and Application),1996,8(3):402-407
[5]陈骏如,李瑞祥,韩银仙等,气相法苯胺N-烷基化反应研究,化学研究与应用(Chemical Research and Application) ,1997,9(1):15-19
[6]杨林涛,许鸿生,黄刚等,常压气固多相催化下苯胺N-烷基化研究,Natural Science Journal of Xiangtan University,1999,3(1):86-92
[7]李速延,周晓奇,苯胺生产技术研究进展,工业催化(INDUSTRIAL CATALYSIS),2006,14(12):7-10
[8] Sankarasubbier Narayanan, Kiranmayi Deshpande, Mechanism of aniline alkylation over vanadia and supported vanadia. Journal of Molecular Catalysis A:Chemical, 1995,104:L109-L113
[9] A.M.Brouwer, Ab Initio Study of the Structures and Vibrational Spectra of Some Diamine Radical Cations. J.Phys.Chem.A ,1997,101(19):3626-3633
[10] V.R. Choudhary, P.Devadas, A.K.Kinage, Influence of binder on the acidity and performance of H-Gallosilicate(MFI) zeolite in propane aromatization. Applied Catalysis A:General, 1997,162:223-233
[11] M.Campanati, P.Savini,A.Tagliani, Environmentally friendly vapour phase synthesis of alkylquinolines. Catalysis Letters, 1997,47:247-250
[12] Z. Hoemann Michael, Anita Melikian-Badalian, G..Kumaravel, Solid-Phase Synthesis of Substituted Quinoline and Isoquinoline Derivatives Using Heterocyclic N-oxide Chemistry. Tetrahedron Letters, 1998,39:4749-4752
[13] Mih?ly Bart?k, Andr?s F?si, Ferenc Notheisz, The mechanism of hydrogenolysis and isomerization of oxacycloalkanes on metals XV. Transformation of ethyl- and vinyloxirane on Cu–SiO2. Journal of Molecular Catalysis A: Chemical, 1998,135:307–316
[14] F.M. Bautista, J.M. Campelo, A. Garcia, D. Luna, J.M. Marinas, A.A. Romero, N-Alkylation of aniline with methanol over AlPO4-Al203 catalysts. Applied Catalysis A: General, 1998, 166:39-45
[15] Basude Manohar, Ibram Ganesh, Benjaram M.Reddy, Aniline synthesis from cyclohexanol and ammonia over mixed oxide catalysts. Journal of MolecularCatalysis A:Chemical, 1998,129:L5-L8
[16] H.M. Sampath Kumar, B.V. Subba Reddy, S.Anjaneyulu, A Novel and Efficient Approach to Mono-N-Alkyl Anilines via Addition of Grignard Reagents to Aryl Azides. Tetrahedron Letters, 1999,40:8305-8306
[17] Mar?aángeles Aramend?a, V?ctor Borau, César Jiménez, JoséMar?a Marinas, Francisco JoséRomero, N-alkylation of aniline with methanol over magnesium phosphates. Applied Catalysis A: General, 1999, 183 :73-80
[18] V. Radha Rani, N. Srinivas, S.J. Kulkarni, K.V. Raghavan, Amino cyclization of terminal (α,ω)-diols over modified ZSM-5 catalysts. Journal of Molecular Catalysis A: Chemical, 2002,187: 237–246
[19] R. Anand, S.S. Khaire, R. Maheswari, K.U. Gore, V.R. Chumbhale, N-Alkylation of aniline with ethanol over HY and dealuminated HY zeolites. Applied Catalysis A: General, 2003, 242: 171–177
[20] Fujita Ken-ichi, Li Zhenzi, Ozeki Naohiro, N-Alkylation of amines with alcohols catalyzed by a Cp*Ir complex. Tetrahedron Letters, 2003,44:2687-2690
[21] J.H.Paden, H.Adkins, The Synthesis of Pyrrolidines, Piperidines and Hexahydroazepines. J.Am.Chem.Soc, 1936,58:2487-2499
[22] Sakurai, Electrolytic Reduction of Glutarimide and Its Derivatives. Bull. Chem. Soc. Japan, 1938,13(7):482-488
[23] Roger Adams, J.E.Mahan, Basicity Studies of Tertiary Vinyl Amines. Bull. Chem. Soc. Japan, 1942,64:2588-2593
[24] H.A.Sommers, S.E.Aaland, The Reaction of 1,5-Dibromopentane with o-Substituted Anilines. The Synthesis of 1-Arylpiperidines. J.Am.Chem.Soc, 1953,75:5280-5284
[25] H.A.Sommers,TheReaction of Dibromoalkanes and o-(Bromoalkyl)-α-bromotoluenes with o-Substituted Anilines.The Synthesis of 1-Arylp yrrolidines and Related Compounds. J.Am.Chem.Soc, 1956,78(6):2439-2445
[26] H.Yamamoto, K.Maruoka, Novel N-Alkylation of Amines with Organocopper Reagents. J.Org.Chem.,1980,45,2739-2740
[27] M.D.Rozeboom., K.N. Houk, S. Searles, Photoelectron Spectroscopy of N-Aryl Cyclic Amines.Variable Conformations and Relationships to Gas- and Solution-Phase Basicities. J.Am.Chem.Soc, 1982,104(12):3448-3453
[28] Anna Diez, Aline Voldoire, Isabel L6pez, and Mario Rubiralta, Synthetic Applications of 2-Aryl-4-piperidones, X Synthesis of 3-Aminopiperidines, Potential Substance P Antagonists. Tetrahedron, 1995,51(17): 5143-5156
[29] Henrik Franzyk, Signe M. Frederiksen, and S?ren Rosendal Jensen, Synthesis of Monoterpene Piperidines from the Iridoid Glucoside Antirrhinoside. J.Nat. Prod., 1997, 60(10):1012-1016
[30] P. Verevkin Sergey , Thermochemistry of Amines: Experimental Standard Molar Enthalpies of Formation of N-Alkylated Piperidines. Structural Chemistry,1998,9(2):113-119
[31] Mariappan Periasamy, K. Natarajan Jayakumar, and Pandi Bharathi, Aryltitanium Species through the Reaction of N,N-Dialkylarylamines with TiCl4: Oxidative Coupling, N-Dealkylation, and Reaction with Electrophiles. J. Org. Chem., 2000, 65(11), 3548-3550
[32] Ramaiah Kumareswaran, Thiagarajan Balasubramanian and Alfred Hassner, Synthesis of enantiopure pyrrolidine and piperidine derivatives via ring closing metathesis. Tetrahedron Letters, 2000, 41: 8157–8162
[33] Christophe Morice, Mathias Domostoj, Karin Briner, Synthesis of constrained arylpiperidines using intramolecular Heck or radical reactions. Tetrahedron Letters, 2001,42: 6499–6502
[34] Alain Merschaert, Laurent Delhaye, Jean-Paul Kestemont, New stereoselective syntheses of cis- and trans-2-methyl-4-arylpiperidines. Tetrahedron Letters, 2003,44:4531–4534
[35] M. Weintraub Philip, S. Sabol Jeffrey, M. Kane John , Recent advances in the synthesis of piperidones and piperidines. Tetrahedron, 2003,59:2953–2989
[36] G. P. Buffat Maxime, Synthesis of piperidines. Tetrahedron, 2004, 60 :1701–1729
[37] Alexandru Gheorghe, Beatrice Quiclet-Sire, Xavier Vila and Samir Z. Zard, Synthesis of substituted 3-arylpiperidines and 3-arylpyrrolidines by radical 1,4 and 1,2-aryl migrations. Tetrahedron, 2007, 63:7187–7212
[38] Fabio Bellina and Renzo Rossi, Synthesis and biological activity of pyrrole, pyrroline and pyrrolidine derivatives with two aryl groups on adjacent positions. Tetrahedron, 2006,62 :7213–7256
[39] German Nadezhda, W. Kaatz Glenn and J. Kerns Robert, Synthesis and evaluation of PSSRI-based inhibitors of Staphylococcus aureus multidrug efflux pumps. Bioorganic & Medicinal Chemistry Letters, 2008, 18: 1368–1373
[40] V.P.Khilya, S.P.Bondarenko, A.V.Turov, SYNTHESIS OF PYRIDINE AND QUINOLINE ANALOGS OF CHALCONE. STUDY OF THEIR STRUCTURE BY THE PMR METHOD, Chemistry of Heterocyclic Compounds, 1998,34(5):587-591
[41] M. Campanati, A. Vaccari, O. Piccolo , Environment-friendly synthesis of nitrogen-containing heterocyclic compounds. Catalysis Today, 2000, 60:289–295
[42] B. Satyavathi, A.N. Patwari, M. Bhagwanth Rao, Regio-selective catalytic vapor phase alkylation of aniline: preparation of 2,6-diethylaniline. Applied Catalysis A: General, 2003,246:151–160
[43] K. Nishamol, K.S. Rahna, S. Sugunan, Selective alkylation of amine to N-methyl aniline using chromium manganese ferrospinels. Journal of Molecular Catalysis A: Chemical, 2004,209: 89–96
[44] V. D. Stytsenko, Tao Do Huu, and V. A. Vinokurov, Catalytic Alkylation of Aniline with Methanol. Kinetics and Catalysis, 2005,46(3):376–379
[45] Zhang Jing , Leitus Gregory, Yehoshoa Ben-David, Facile Conversion of Alcohols into Esters and Dihydrogen Catalyzed by New Ruthenium Complexes, J.Am.Chem.Soc, 2005,127:10840-10841
[46] Zhu Di, Wang Rongliang, Mao Jincheng, Efficient copper-catalyzed amination of aryl halides with amines and N-H heterocycles using rac-BINOL as ligand. Journal of Molecular Catalysis A: Chemical, 2006,256:256–260
[47] Sipra Naskar, Manish Bhattacharjee,Selective N-monoalkylation of anilines catalyzed by a cationic ruthenium(Ⅱ) compound. Tetrahedron Letters, 2007,48:3367-3370
[48] K. Felf?ldi, M. S.Klyavlin, M.Bartók, Transformation of organic compounds in the presence of metal complexes V. Cyclization of aminoalcohols on a ruthenium complex. Journal of Organometallic Chemistry, 1989,362(1-2), 193-195;
[49] Koelsch and Carney, Hydrogenation of Hydroxyglutaconaldehyde Dianil and of 3- Hydroxy-1-phenylpyridinium Salts. J.Am.Chem.Soc.,1950,72:2285-2286
[50] C. H. Horning, F. W. Bergstrom, The Action of Bases on Organic Halogen Compounds. IV. The Action of the Lithium Salts of Aliphatic Amines on some Organic Halogen Compounds. Journal of the American Chemical Society, 1945,67(12):2110-2111;
[51] J. Bunnett, T. Brotherton, Notes - Preparation of Dialkylanilines by the Reaction of Bromobenzene with Sodium Amide and Dialkylamines. Journal of Organic Chemistry, 1957,22(7):832-834;
[52] J. V. Bhaskar Kanth, Mariappan Periasamy, Convenient procedure for N-phenylation of amines. Journal of Organic Chemistry, 1993,58(11):3156-7;
[53] Eric Brenner and Yves Fort, New Efficient Nickel(0) Catalysed Amination of Aryl Chlorides. Tetrahedron Letters, 1998,39: 5359-5362
[54] R.Buchmeiser Michael and K.Wurst,Access to Well-Defined Heterogeneous Catalytic Systems via Ring-Opening Metathesis Polymerization (ROMP):Applications in Palladium(II)-Mediated Coupling Reactions. Journal of the American Chemical Society, 1999, 121(48):11101-11107;
[55] Laurent Djakovitch, Michael Wagner and Klaus K?hler, Amination of aryl bromides catalysed by supported palladium. Journal of Organometallic Chemistry, 1999,592(2):225-234;
[56] Shi Lei, Wang Min, Fan Chun-An, Zhang Fu-Min, and Tu Yong-Qiang, Rapid and Efficient Microwave-Assisted Amination of Electron-Rich Aryl Halides without a Transition-Metal Catalyst. Organic Letters, 2003,5(19):3515-3517;
[57] S. Gajare Anil,Toyota Kozo,Yoshifuji Masaaki and Ozawa Fumiyuki, Application of a diphosphinidenecyclobutene ligand in the solvent-free copper-catalysed amination reactions of arylhalides. Chemical Communications (Cambridge, United Kingdom), 2004,(17):1994-1995;
[58] Lange Ben de, H.Lambers-Verstappen Marielle, Aromatic Amination of ArylBromides Catalysed by Copper/β-Diketone Catalysts:The Effect of Concentration. Synlett, 2006, 2006 (18):3105-3109;
[59] Le Gall Erwan, Gosmini Corinne and Troupel Michel, Aromatic organozinc reagents as nucleophiles in theα-arylation of piperidine and tetrahydropyran. Tetrahedron Letters, 2006,47(4):455-458;
[60] M. Lakshmi Kantam, G.T. Venkanna, Ch. Sridhar and K.B. Shiva Kumar, Copper fluorapatite catalyzed N-arylation of heterocycles with bromo and iodoarenes. Tetrahedron Letters, 2006,47(23): 3897-3899;
[61] Israel Conesa Lerma, Mark J. Cawley, F. Geoffrey N. Cloke, Katherine Arentsen, James S. Scott, Stuart E. Pearson, John Hayler and Stephen Caddick, Studies on Pd/imidazolium salt protocols for aminations of aryl bromides and iodides using lithium hexamethyldisilazide (LHMDS). Journal of Organometallic Chemistry, 2005, 690(24-25): 5841-5848
[62] Noemi Cabello-Sanchez, Ludovic Jean, Jacques Maddaluno, Marie-Claire Lasne, and Jacques Rouden, Palladium-Mediated N-Arylation of Heterocyclic Diamines: Insights into the Origin of an Unusual Chemoselectivity. Journal of Organic Chemistry, 2007,72(6):2030-2039;
[63] Reddy Nagavelli Prabhakar and Tanaka Masato, Palladium-catalyzed amination of aryl chlorides. Tetrahedron Letters, 1997, 38(27): 4807-4810;
[64] Eric Brenner and Yves Fort, New efficient nickel(0) catalysed amination of aryl chlorides. Tetrahedron Letters, 1998, 39(30): 5359-5362;
[65] Eric Brenner, Rapha?l Schneider and Yves Fort, Nickel-catalysed couplings of aryl chlorides with secondary amines and piperazines. Tetrahedron, 1999, 55(44): 12829-12842;
[66] Benot Gradel, Eric Brenner, Rapha?l Schneider and Yves Fort, Nickel-catalysed amination of aryl chlorides using a dihydroimidazoline carbene ligand. Tetrahedron Letters, 2001, 42(33): 5689-5692;
[67] Matthias Beller, Claudia Breindl, Thomas H. Riermeier and Annegret Tillack, Synthesis of 2,3-Dihydroindoles, Indoles and Anilines by Transition Metal-Free Amination of Aryl Chlorides. Journal of Organic Chemistry, 2001, 66(4): 1403-1412;
[68] Y. Li George, Zheng Gang and F. Noonan Andrew, Highly Active, Air-Stable Versatile Palladium Catalysts for the C?C, C?N and C?S Bond Formations via Cross-Coupling Reactions of Aryl Chlorides. Journal of Organic Chemistry, 2001, 66(25): 8677-8681;
[69] R.Buchmeiser Michael,Thomas Schareina,Rhett Kempe and Klaus Wurst, Bis(pyrimidine)-based palladium catalysts: synthesis, X-ray structure and applications in Heck–, Suzuki–, Sonogashira–Hagihara couplings and amination reactions. Journal of Organometallic Chemistry, 2001, 634(1): 39-46;
[70] Andreas Ehrentraut, Alexander Zapf and Matthias Beller, A new improved catalystfor the palladium-catalyzed amination of aryl chlorides. Journal of Molecular Catalysis A: Chemical, 2002, 182-183: 515-523;
[71] Anil S. Gajare, Kozo Toyota, Masaaki Yoshifuji and Fumiyuki Ozawa, Application of a diphosphinidenecyclobutene ligand in the solvent-free copper-catalysed amination reactions of aryl halides. Chemical Communications (Cambridge, United Kingdom), 2004, 2004 (17):1994-1995;
[72] L. J. Goo?en, J. Paetzold, O. Briel, A. Rivas-Nass, R. Karch, B. Kayser, Buchwald-Hartwig Aminations of Aryl Chlorides:A Practical Protocol Based on Commercially Available Pd(0)-NHC Catalysts. Synlett, 2005, 2005(02): 275-278;
[73] Lange Ben de, H. Lambers-Verstappen Marielle, Lizette Schmieder-van de Vondervoort, Natascha Sereinig, Ron de Rijk, AndréH. M. de Vries, Johannes G. de Vries, Aromatic Amination of Aryl Bromides Catalysed by Copper/β-Diketone Catalysts:The Effect of Concentration. Synlett, 2006, 2006(18): 3105-3109;
[74] Chen Chen and Yang Lian-Ming, Ni(II)?(σ-Aryl) Complex:A Facile, Efficient Catalyst for Nickel-Catalyzed Carbon?Nitrogen Coupling Reactions. Journal of Organic Chemistry, 2007, 72(16): 6324-6327;
[75] Sasmita Tripathy, Richard LeBlanc, Tony Durst, Formation of 2-Substituted Iodobenzenes from Iodobenzene via Benzyne and Ate Complex Intermediates. Organic Letters, 1999, 1(12): 1973-1975;
[76] Kang Suk-Ku, Lee Sang-Ho, Lee Duckhee, Copper-Catalyzed N-Arylation of Amines with Hypervalent Iodonium Salts. Synlett, 2000, 2000 (07): 1022-1024;
[77] Kwong Fuk Yee, Klapars Artis, L. Buchwald Stephen, Copper-Catalyzed Coupling of Alkylamines and Aryl Iodides: An Efficient System Even in an Air Atmosphere. Organic Letters, 2002, 4(4): 581-584;
[78] Ma Dawei, Cai Qian, Zhang Hui, Mild Method for Ullmann Coupling Reaction of Amines and Aryl Halides. Organic Letters, 2003, 5(14): 2453-2455;
[79] Zhang Zhanjin, Mao Jincheng, Zhu Di,Wu Fan, Chen Huilin and Wan Boshun, Highly efficient copper-catalyzed N-arylation of alkylamines with aryl iodides using phosphoramidite as ligand. Catalysis Communications, 2005, 6(12): 784-787;
[80] Israel Conesa Lerma, Mark J. Cawley, F. Geoffrey N. Cloke, Katherine Arentsen, James S. Scott, Stuart E. Pearson, John Hayler and Stephen Caddick, Studies on Pd/imidazolium salt protocols for aminations of aryl bromides and iodides using lithium hexamethyldisilazide (LHMDS). Journal of Organometallic Chemistry, 2005, 690(24-25): 5841-5848;
[81] Zhang Hui, Cai Qian, Ma Dawei, Amino Acid Promoted CuI-Catalyzed C?N Bond Formation between Aryl Halides and Amines or N-Containing Heterocycles. Journal of Organic Chemistry, 2005, 70(13): 5164-5173;
[82] S.Yadav Lal Dhar, S.Yadav Beerendra, K.Rai Vijai, Active-Copper-Promoted Expeditious N-Arylations in Aqueous Media under Microwave Irradiation. Synthesis,2006, 2006 (11): 1868-1872;
[83] Zhang Zhanjin, Mao Jincheng, Zhu Di, Wu Fan, Chen Huilin and Wan Boshun, Highly efficient and practical phosphoramidite–copper catalysts for amination of aryl iodides and heteroaryl bromides with alkylamines and N(H)-heterocycles. Tetrahedron, 2006, 62(18): 4435-4443;
[84] Zhu Di, Wang Rongliang, Mao Jincheng, Xu Lei, Wu Fan and Wan Boshun, Efficient copper-catalyzed amination of aryl halides with amines and N-H heterocycles using rac-BINOL as ligand. Journal of Molecular Catalysis A: Chemical, 2006, 256(1-2): 256-260;
[85] Yang Minghua and Liu Fei, An Ullmann Coupling of Aryl Iodides and Amines Using an Air-Stable Diazaphospholane Ligand. Journal of Organic Chemistry, 2007, 72(23): 8969-8971;
[86] Laxmidhar Rout, Suribabu Jammi, T. Punniyamurthy, Novel CuO Nanoparticle Catalyzed C?N Cross Coupling of Amines with Iodobenzene. Organic Letters, 2007, 9(17): 3397-3399;
[87] Guo Diliang, Huang He, Xu Jinyi, Jiang Hualiang and Liu Hong, Efficient Iron-Catalyzed N-Arylation of Aryl Halides with Amines. Organic Letters, 2008, 10(20): 4513-4516;
[88] Wittig and Merkle, Ber., 1943, 76, 109
[89] Le Fevre, Preparatin and Dinitration of 1-Phenylpiperidine. J.Chem.Soc.,1932, 1376-1379
[90] R. Katritzky Alan, Fan Weiqiang, The chemistry of benzotriazole.A novel and versatile synthesis of 1-alkyl-, 1-aryl-, 1-(alkylamino)-, or 1-amido-substituted and of 1,2,6-trisubstituted piperidines from glutaraldehyde and primary amines or monosubstituted hydrazines. Journal of Organic Chemistry, 1990, 55(10): 3205-3209;
[91] M. Berman Ashley, S. Johnson Jeffrey, Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents. Journal of the American Chemical Society, 2004, 126(18): 5680-5681;
[92] M. Berman Ashley, M. Berman Jeffrey, Nickel-Catalyzed Electrophilic Amination of Organozinc Halides. Synlett, 2005, 2005 (11): 1799-1801;
[93] M. Berman Ashley, S. Johnson Jeffrey, Copper-Catalyzed Electrophilic Amination of Organozinc Nucleophiles: Documentation of O-Benzoyl Hydroxylamines as Broadly Useful R2N(+) and RHN(+) Synthons. Journal of Organic Chemistry, 2006, 71(1): 219-224;
[94] J.Campbell Matthew, S.Johnson Jeffrey, Mechanistic Studies of the Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents and Development of a Zinc-Free Protocol. Organic Letters, 2007, 9(8): 1521-1524;
[95] Ishikawa Teruhiko, Uedo Eiji, Tani Rie and Saito Seiki, Aromatization of Enamines Promoted by a Stoichiometric Amount of Palladium(II) Salts: A Novel Method for theSynthesis of Aromatic Amines. Journal of Organic Chemistry, 2001, 66(1): 186-191
[96] Srinivas Gadthula, Periasamy Mariappan, Aromatization of enamines using the TiCl4/Et3N reagent system. Tetrahedron Letters, 2002, 43(15): 2785-2788
[97] D. Quach Tan, A. Batey Robert, Ligand- and Base-Free Copper(II)-Catalyzed C?N Bond Formation:Cross-Coupling Reactions of Organoboron Compounds with Aliphatic Amines and Anilines. Organic Letters, 2003, 5(23): 4397-4400
[98] M. Lakshmi Kantam, B. Neelima, Ch. Venkat Reddy and V. Neeraja, N-Arylation of imidazoles, imides, amines, amides and sulfonamides with boronic acids using a recyclable Cu(OAc)2·H2O/[bmim][BF4] system. Journal of Molecular Catalysis A: Chemical, 2006, 249(1-2): 201-206;
[99] Sreedhar Bojja, T.Venkanna Gopaladasu, Kota Balaji Shiva Kumar, Vura Balasubrahmanyam, Copper(I) Oxide Catalyzed N-Arylation of Azoles and Amines with Arylboronic Acid at Room Temperature under Base-Free Conditions. Synthesis, 2008, 2008(05): 795-799;
[100] Xu Gang, Wang Yan-Guang, Microwave-Assisted Amination from Aryl Triflates without Base and Catalyst. Organic Letters, 2004, 6(6): 985-987
[101] Gao Cai-Yan, Yang Lian-Ming, Nickel-Catalyzed Amination of Aryl Tosylates. Journal of Organic Chemistry, 2008, 73(4): 1624-1627;
[102] M. Berman Ashley, S. Johnson Jeffrey, Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents. Journal of the American Chemical Society, 2004, 126(18): 5680-5681;
[103] M. Berman Ashley, S. Johnson Jeffrey, Copper-Catalyzed Electrophilic Amination of Organozinc Nucleophiles: Documentation of O-Benzoyl Hydroxylamines as Broadly Useful R2N(+) and RHN(+) Synthons. Journal of Organic Chemistry, 2006, 71(1): 219-224
[104] A. Miller Joseph, W. Dankwardt John, M. Penney Jonathan, Nickel Catalyzed Cross-Coupling and Amination Reactions of Aryl Nitriles. Synthesis, 2003, 2003 (11): 1643-1648;
[105] Christophe Desmarets, Rapha?l Schneider, Yves Fort, Nickel-mediated amination chemistry. Part 1: Efficient aminations of (het)aryl 1,3-di and 1,3,5-trichlorides. Tetrahedron Letters, 2000, 41(16): 2875-2879;
[106] P. Beletskaya Irina, G..Bessmertnykh Alla, Roger Guilard, Palladium-catalyzed amination of aryl dibromides with secondary amines: synthetic and mechanistic aspects. Tetrahedron Letters, 1999, 40(35): 6393-6397;
[107] H. R. Barton Derek, Finet Jean-Pierre, Khamsi Jamal, Copper salts catalysis of N-phenylation of amines by trivalent organobismuth compounds. Tetrahedron Letters, 1987, 28(8): 887-90;
[108] Sakurai, Bull.Chem.Soc. Japan, 1938, 13(7): 482-488
[109] L. Romera Juan, M. Cid José, A. Trabanco Andrés, Potassium iodide catalysedmonoalkylation of anilines under microwave irradiation. Tetrahedron Letters, 2004, 45: 8797–8800
[110] Ju Yuhong,S. Varma Rajender, An Efficient and Simple Aqueous N-Heterocyclization of Aniline Derivatives: Microwave-Assisted Synthesis of N-Aryl Azacycloalkanes. Org. Lett., 2005, 7(12): 2409-2411
[111] Ju Yuhong,S. Varma Rajender, Aqueous N-Heterocyclization of Primary Amines and Hydrazineswith Dihalides: Microwave-Assisted Syntheses of N-Azacycloalkanes, Isoindole, Pyrazole, Pyrazolidine and Phthalazine Derivatives. J. Org. Chem., 2006, 71(1): 135-141
[112] T. Michael Barnard, Grace S. Vanier, Michael J. Collins, Scale-Up of the Green Synthesis of Azacycloalkanes and Isoindolines under Microwave Irradiation. Organic Process Research & Development, 2006, 10(6): 1233-1237
[113] Periasamy Mariappan, K. Jayakumar Natarajan, Bharathi Pandi, Aryltitanium Species through the Reaction of N,N-Dialkylarylamines with TiCl4: Oxidative Coupling, N-Dealkylation, and Reaction with Electrophiles. Journal of Organic Chemistry, 2000, 65(11): 3548-3550
[114] B.Singh Chingakham, Kavala Veerababurao, K.Samal Akshaya, Patel Bhisma K., Aqueous-Mediated N-Alkylation of Amines. European Journal of Organic Chemistry, 2007, 2007 (8): 1369-1377
[115] A. N. Bourns, 1-PHENYLPIPERIDINE. Organic Syntheses, Coll. 1963, 4: 795; 1954, 34, 79
[116] Robert E.Walkup, Searles Scott, Synthesis of sterically hindered 1-arylpyrrolidines and 1-arylpiperidines by condensation of primary aromatic amines with cyclic ethers or diols. Tetrahedron, 1985, 41(1): 101-106
[117] S. Gajare Anil, Kozo Toyota, Masaaki Yoshifuji, Fumiyuki Ozawa, Solvent Free Amination Reactions of Aryl Bromides at Room Temperature Catalyzed by a (π-Allyl) palladium Complex Bearing a Diphosphinidenecyclobutene Ligand. Journal of Organic Chemistry, 2004, 69(19): 6504-6506
[118] Y. Watanabe, S.C.Shim, T. Mitaudo, M.Yamashita, Y. Takegami, The Facile Synthesis of N-Substituted piperidines from Glutaraldehyde and Primary Amines with Tetracarbonylhydridoferrate. Bull. Chem. Soc. Jpn., 1976, 49(8): 2302-2305
[119] Verardo Giancarlo,Dolce Anna ,Toniutti Nicoletta,Reductive One Batch Synthesis of N-Substituted Pyrrolidines from Primary Amines and 2,5-Dimethoxytetrahydrofuran. Synthesis, 1999, 1999(01): 74-79
[120] R.Katritzky Alan, Fan Weiqiang, The chemistry of benzotriazole. A novel and versatile synthesis of 1-alkyl-, 1-aryl-, 1-(alkylamino)-, or 1-amido-substituted and of 1,2,6-trisubstituted piperidines from glutaraldehyde and primary amines or monosubstituted hydrazines. Journal of Organic Chemistry, 1990, 55(10): 3205-3209
[121] Suwa Toshihiro, Sugiyama Erika, Shibata Ikuya, Baba Akio, ChemoselectiveReductive Amination of Aldehydes and Ketones by Dibutylchlorotin Hydride-HMPA Complex. Synthesis, 2000, 2000 (06): 789-800
[122] Verardo Giancarlo, Angelo G. Giumanini, Favret Grazia, Strazzolini Paolo, Reductive One Batch Synthesis of N-Arylpiperidines From Primary Amines and Glutaraldehyde. Synthesis, 1991, 1991(06): 447-450;
[123] Reynolds and Kenyon, J.Am.Chem.Soc., 1950, 72: 1597-1598
[124] Tsuji Yasushi, Huh Keun-Tae, Ohsugi Yukihiro, Watanabe Yoshihisa, Ruthenium Complex Catalyzed N-Heterocyclization. Syntheses of N-Substituted Piperidines, Morpholines, and Piperazines from Amines and 1,5-Diols. J. Org. Chem., 1985, 50(9): 1365-1370
[125] K.Felf?ldi, M.S. Klyavlin and M.Bartók, Transformation of organic compounds in the presence of metal complexes V*. Cyclization of aminoalcohols on a ruthenium complex. Journal of Organometallic Chemistry, 1989, 362(1-2): 193-195
[126] RobA.T.M.Abbenhuis,Jaap.Boersma,Gerard.van,Koten,Ruthenium-Complex-Catalyzed N-(Cyclo)alkylation of Aromatic Amines with Diols. Selective Synthesis of N-(ω-Hydroxyalkyl) anilines of Type PhNH(CH2)nOH and of Some Bioactive Arylpiperazines. J. Org. Chem., 1998, 63(13): 4282-4290
[127] S.A.Hamid Malai Haniti, M.J.Williams Jonathan, Ruthenium catalysed N-alkylation of amines with alcohols, Chem. Commun, 2007: 725–727
[128] G . Ecke George, P. Napolitano John, H. Filbey Allen, ortho-Alkylation of Aromatic Amines. J.Org.Chem., 1957, 22: 639-642
[129] Frédéric Valot, Fabienne Fache, Roland Jacquot, Michel Spagnol and Marc Lemaire, Gas-phase selective N-alkylation of amines with alcohols overγ-alumina. Tetrahedron Letters, 1999, 40: 3689-3592
[130] Sankarasubbier Narayanan, Kiranmayi Deshpande, Aniline alkylation over solid acid catalysts. Applied Catalysis A: General, 2000, 199: 1–31
[131] D.Yadav Ganapati, S.Doshi Nirav, Alkylation of aniline with methyl-tert-butyl ether (MTBE) and tert-butanol over solid acids: product distribution and kinetics. Journal of Molecular Catalysis A: Chemical, 2003, 194: 195–209
[132] Yur’ev, Yu. K, Prokina.M.N., J.Gen.Chem.USSR 7, 1938,1868; Chem.Abstr., 1938, 32: 548
[133] Charles A. Bordner, Charles G. Karmin, Niagara Falls., Production of pyrrolidine. [P]US:2525584, 1950, 10: 10
[134] L.Meszaros. et al, Acta Univ. Szegedienesis Acta Phys. et Chem.[N.S.], 1958, 4: 144-152
[135] H.Vaserrnans, S.Hillers, A.Avots, The preparation of new ganglion-blocking agents“pentapyrrolidine”and“tetrapiperdine”[J], Latvijas PSP Zinatnu Akad. Vestis., 1958, 5: 79-86
[136] Fujita K, Hatada K, Ono Y. et al, Ring transformation of tetrahydrofuran intopyrrolidine over synthetic zeolite[J]. J.Catal., 1974, 35: 325
[137] Kou Hatada, Massatoshi Shimada, Katsuhiro Fujita, et al., Ring transformations of oxygen containing heterocycles into nitrogen containing heterocycles over synthetic zeolites[J]. Chem Lett, 1974: 439-442
[138] Yoshio Ono, Kou Hatada, Katsuhiro Fujita, et al., Type L zeolites as selective catalysts for the ring transformation of cylic ethers into cyclic lmines[J]. J.Catal., 1976, 41: 322
[139] Nomura M, Tomogane T, Kikkawa S, et al., Exchange reaction of tetrahydrofuran to pyrrolidine with ammonia over supported transition metalchloride catalysts[J]. Sekiyu Gakkai Shi, 1977, 20(5): 419-422
[140] Iwasaki Mineyuki, Production of parrolidine [P]. JP:1268681, 1989, 10: 26
[141] An Nan Ko, Ching ling Yang, Applied Catalysis A:General, 1996, 134: 53-56
[142]甄开吉等主编,催化作用基础.北京:科学出版社,2005.284~288
[143]黄仲涛主编,工业催化.北京:化学工业出版社,1994. 99
[144]王桂茹主编,催化剂与催化作用.大连.大连理工大学出版社,2000. 324
[145]高正中编,实用催化.北京:化学工业出版社,1996. 191~192
[2]石雷,由苯胺和乙二醇一步催化合成吲哚的研究:[博士学位论文].大连:大连理工大学,2002,
[3]殷福珊,陈银广,刘学民等,脂肪醇的胺化反应,日用化学工业,1996年第4期
[4]唐靖,陈骏如,李瑞祥等,芳胺常压气相N-烷基化反应研究,化学研究与应用(Chemical Research and Application),1996,8(3):402-407
[5]陈骏如,李瑞祥,韩银仙等,气相法苯胺N-烷基化反应研究,化学研究与应用(Chemical Research and Application) ,1997,9(1):15-19
[6]杨林涛,许鸿生,黄刚等,常压气固多相催化下苯胺N-烷基化研究,Natural Science Journal of Xiangtan University,1999,3(1):86-92
[7]李速延,周晓奇,苯胺生产技术研究进展,工业催化(INDUSTRIAL CATALYSIS),2006,14(12):7-10
[8] Sankarasubbier Narayanan, Kiranmayi Deshpande, Mechanism of aniline alkylation over vanadia and supported vanadia. Journal of Molecular Catalysis A:Chemical, 1995,104:L109-L113
[9] A.M.Brouwer, Ab Initio Study of the Structures and Vibrational Spectra of Some Diamine Radical Cations. J.Phys.Chem.A ,1997,101(19):3626-3633
[10] V.R. Choudhary, P.Devadas, A.K.Kinage, Influence of binder on the acidity and performance of H-Gallosilicate(MFI) zeolite in propane aromatization. Applied Catalysis A:General, 1997,162:223-233
[11] M.Campanati, P.Savini,A.Tagliani, Environmentally friendly vapour phase synthesis of alkylquinolines. Catalysis Letters, 1997,47:247-250
[12] Z. Hoemann Michael, Anita Melikian-Badalian, G..Kumaravel, Solid-Phase Synthesis of Substituted Quinoline and Isoquinoline Derivatives Using Heterocyclic N-oxide Chemistry. Tetrahedron Letters, 1998,39:4749-4752
[13] Mih?ly Bart?k, Andr?s F?si, Ferenc Notheisz, The mechanism of hydrogenolysis and isomerization of oxacycloalkanes on metals XV. Transformation of ethyl- and vinyloxirane on Cu–SiO2. Journal of Molecular Catalysis A: Chemical, 1998,135:307–316
[14] F.M. Bautista, J.M. Campelo, A. Garcia, D. Luna, J.M. Marinas, A.A. Romero, N-Alkylation of aniline with methanol over AlPO4-Al203 catalysts. Applied Catalysis A: General, 1998, 166:39-45
[15] Basude Manohar, Ibram Ganesh, Benjaram M.Reddy, Aniline synthesis from cyclohexanol and ammonia over mixed oxide catalysts. Journal of MolecularCatalysis A:Chemical, 1998,129:L5-L8
[16] H.M. Sampath Kumar, B.V. Subba Reddy, S.Anjaneyulu, A Novel and Efficient Approach to Mono-N-Alkyl Anilines via Addition of Grignard Reagents to Aryl Azides. Tetrahedron Letters, 1999,40:8305-8306
[17] Mar?aángeles Aramend?a, V?ctor Borau, César Jiménez, JoséMar?a Marinas, Francisco JoséRomero, N-alkylation of aniline with methanol over magnesium phosphates. Applied Catalysis A: General, 1999, 183 :73-80
[18] V. Radha Rani, N. Srinivas, S.J. Kulkarni, K.V. Raghavan, Amino cyclization of terminal (α,ω)-diols over modified ZSM-5 catalysts. Journal of Molecular Catalysis A: Chemical, 2002,187: 237–246
[19] R. Anand, S.S. Khaire, R. Maheswari, K.U. Gore, V.R. Chumbhale, N-Alkylation of aniline with ethanol over HY and dealuminated HY zeolites. Applied Catalysis A: General, 2003, 242: 171–177
[20] Fujita Ken-ichi, Li Zhenzi, Ozeki Naohiro, N-Alkylation of amines with alcohols catalyzed by a Cp*Ir complex. Tetrahedron Letters, 2003,44:2687-2690
[21] J.H.Paden, H.Adkins, The Synthesis of Pyrrolidines, Piperidines and Hexahydroazepines. J.Am.Chem.Soc, 1936,58:2487-2499
[22] Sakurai, Electrolytic Reduction of Glutarimide and Its Derivatives. Bull. Chem. Soc. Japan, 1938,13(7):482-488
[23] Roger Adams, J.E.Mahan, Basicity Studies of Tertiary Vinyl Amines. Bull. Chem. Soc. Japan, 1942,64:2588-2593
[24] H.A.Sommers, S.E.Aaland, The Reaction of 1,5-Dibromopentane with o-Substituted Anilines. The Synthesis of 1-Arylpiperidines. J.Am.Chem.Soc, 1953,75:5280-5284
[25] H.A.Sommers,TheReaction of Dibromoalkanes and o-(Bromoalkyl)-α-bromotoluenes with o-Substituted Anilines.The Synthesis of 1-Arylp yrrolidines and Related Compounds. J.Am.Chem.Soc, 1956,78(6):2439-2445
[26] H.Yamamoto, K.Maruoka, Novel N-Alkylation of Amines with Organocopper Reagents. J.Org.Chem.,1980,45,2739-2740
[27] M.D.Rozeboom., K.N. Houk, S. Searles, Photoelectron Spectroscopy of N-Aryl Cyclic Amines.Variable Conformations and Relationships to Gas- and Solution-Phase Basicities. J.Am.Chem.Soc, 1982,104(12):3448-3453
[28] Anna Diez, Aline Voldoire, Isabel L6pez, and Mario Rubiralta, Synthetic Applications of 2-Aryl-4-piperidones, X Synthesis of 3-Aminopiperidines, Potential Substance P Antagonists. Tetrahedron, 1995,51(17): 5143-5156
[29] Henrik Franzyk, Signe M. Frederiksen, and S?ren Rosendal Jensen, Synthesis of Monoterpene Piperidines from the Iridoid Glucoside Antirrhinoside. J.Nat. Prod., 1997, 60(10):1012-1016
[30] P. Verevkin Sergey , Thermochemistry of Amines: Experimental Standard Molar Enthalpies of Formation of N-Alkylated Piperidines. Structural Chemistry,1998,9(2):113-119
[31] Mariappan Periasamy, K. Natarajan Jayakumar, and Pandi Bharathi, Aryltitanium Species through the Reaction of N,N-Dialkylarylamines with TiCl4: Oxidative Coupling, N-Dealkylation, and Reaction with Electrophiles. J. Org. Chem., 2000, 65(11), 3548-3550
[32] Ramaiah Kumareswaran, Thiagarajan Balasubramanian and Alfred Hassner, Synthesis of enantiopure pyrrolidine and piperidine derivatives via ring closing metathesis. Tetrahedron Letters, 2000, 41: 8157–8162
[33] Christophe Morice, Mathias Domostoj, Karin Briner, Synthesis of constrained arylpiperidines using intramolecular Heck or radical reactions. Tetrahedron Letters, 2001,42: 6499–6502
[34] Alain Merschaert, Laurent Delhaye, Jean-Paul Kestemont, New stereoselective syntheses of cis- and trans-2-methyl-4-arylpiperidines. Tetrahedron Letters, 2003,44:4531–4534
[35] M. Weintraub Philip, S. Sabol Jeffrey, M. Kane John , Recent advances in the synthesis of piperidones and piperidines. Tetrahedron, 2003,59:2953–2989
[36] G. P. Buffat Maxime, Synthesis of piperidines. Tetrahedron, 2004, 60 :1701–1729
[37] Alexandru Gheorghe, Beatrice Quiclet-Sire, Xavier Vila and Samir Z. Zard, Synthesis of substituted 3-arylpiperidines and 3-arylpyrrolidines by radical 1,4 and 1,2-aryl migrations. Tetrahedron, 2007, 63:7187–7212
[38] Fabio Bellina and Renzo Rossi, Synthesis and biological activity of pyrrole, pyrroline and pyrrolidine derivatives with two aryl groups on adjacent positions. Tetrahedron, 2006,62 :7213–7256
[39] German Nadezhda, W. Kaatz Glenn and J. Kerns Robert, Synthesis and evaluation of PSSRI-based inhibitors of Staphylococcus aureus multidrug efflux pumps. Bioorganic & Medicinal Chemistry Letters, 2008, 18: 1368–1373
[40] V.P.Khilya, S.P.Bondarenko, A.V.Turov, SYNTHESIS OF PYRIDINE AND QUINOLINE ANALOGS OF CHALCONE. STUDY OF THEIR STRUCTURE BY THE PMR METHOD, Chemistry of Heterocyclic Compounds, 1998,34(5):587-591
[41] M. Campanati, A. Vaccari, O. Piccolo , Environment-friendly synthesis of nitrogen-containing heterocyclic compounds. Catalysis Today, 2000, 60:289–295
[42] B. Satyavathi, A.N. Patwari, M. Bhagwanth Rao, Regio-selective catalytic vapor phase alkylation of aniline: preparation of 2,6-diethylaniline. Applied Catalysis A: General, 2003,246:151–160
[43] K. Nishamol, K.S. Rahna, S. Sugunan, Selective alkylation of amine to N-methyl aniline using chromium manganese ferrospinels. Journal of Molecular Catalysis A: Chemical, 2004,209: 89–96
[44] V. D. Stytsenko, Tao Do Huu, and V. A. Vinokurov, Catalytic Alkylation of Aniline with Methanol. Kinetics and Catalysis, 2005,46(3):376–379
[45] Zhang Jing , Leitus Gregory, Yehoshoa Ben-David, Facile Conversion of Alcohols into Esters and Dihydrogen Catalyzed by New Ruthenium Complexes, J.Am.Chem.Soc, 2005,127:10840-10841
[46] Zhu Di, Wang Rongliang, Mao Jincheng, Efficient copper-catalyzed amination of aryl halides with amines and N-H heterocycles using rac-BINOL as ligand. Journal of Molecular Catalysis A: Chemical, 2006,256:256–260
[47] Sipra Naskar, Manish Bhattacharjee,Selective N-monoalkylation of anilines catalyzed by a cationic ruthenium(Ⅱ) compound. Tetrahedron Letters, 2007,48:3367-3370
[48] K. Felf?ldi, M. S.Klyavlin, M.Bartók, Transformation of organic compounds in the presence of metal complexes V. Cyclization of aminoalcohols on a ruthenium complex. Journal of Organometallic Chemistry, 1989,362(1-2), 193-195;
[49] Koelsch and Carney, Hydrogenation of Hydroxyglutaconaldehyde Dianil and of 3- Hydroxy-1-phenylpyridinium Salts. J.Am.Chem.Soc.,1950,72:2285-2286
[50] C. H. Horning, F. W. Bergstrom, The Action of Bases on Organic Halogen Compounds. IV. The Action of the Lithium Salts of Aliphatic Amines on some Organic Halogen Compounds. Journal of the American Chemical Society, 1945,67(12):2110-2111;
[51] J. Bunnett, T. Brotherton, Notes - Preparation of Dialkylanilines by the Reaction of Bromobenzene with Sodium Amide and Dialkylamines. Journal of Organic Chemistry, 1957,22(7):832-834;
[52] J. V. Bhaskar Kanth, Mariappan Periasamy, Convenient procedure for N-phenylation of amines. Journal of Organic Chemistry, 1993,58(11):3156-7;
[53] Eric Brenner and Yves Fort, New Efficient Nickel(0) Catalysed Amination of Aryl Chlorides. Tetrahedron Letters, 1998,39: 5359-5362
[54] R.Buchmeiser Michael and K.Wurst,Access to Well-Defined Heterogeneous Catalytic Systems via Ring-Opening Metathesis Polymerization (ROMP):Applications in Palladium(II)-Mediated Coupling Reactions. Journal of the American Chemical Society, 1999, 121(48):11101-11107;
[55] Laurent Djakovitch, Michael Wagner and Klaus K?hler, Amination of aryl bromides catalysed by supported palladium. Journal of Organometallic Chemistry, 1999,592(2):225-234;
[56] Shi Lei, Wang Min, Fan Chun-An, Zhang Fu-Min, and Tu Yong-Qiang, Rapid and Efficient Microwave-Assisted Amination of Electron-Rich Aryl Halides without a Transition-Metal Catalyst. Organic Letters, 2003,5(19):3515-3517;
[57] S. Gajare Anil,Toyota Kozo,Yoshifuji Masaaki and Ozawa Fumiyuki, Application of a diphosphinidenecyclobutene ligand in the solvent-free copper-catalysed amination reactions of arylhalides. Chemical Communications (Cambridge, United Kingdom), 2004,(17):1994-1995;
[58] Lange Ben de, H.Lambers-Verstappen Marielle, Aromatic Amination of ArylBromides Catalysed by Copper/β-Diketone Catalysts:The Effect of Concentration. Synlett, 2006, 2006 (18):3105-3109;
[59] Le Gall Erwan, Gosmini Corinne and Troupel Michel, Aromatic organozinc reagents as nucleophiles in theα-arylation of piperidine and tetrahydropyran. Tetrahedron Letters, 2006,47(4):455-458;
[60] M. Lakshmi Kantam, G.T. Venkanna, Ch. Sridhar and K.B. Shiva Kumar, Copper fluorapatite catalyzed N-arylation of heterocycles with bromo and iodoarenes. Tetrahedron Letters, 2006,47(23): 3897-3899;
[61] Israel Conesa Lerma, Mark J. Cawley, F. Geoffrey N. Cloke, Katherine Arentsen, James S. Scott, Stuart E. Pearson, John Hayler and Stephen Caddick, Studies on Pd/imidazolium salt protocols for aminations of aryl bromides and iodides using lithium hexamethyldisilazide (LHMDS). Journal of Organometallic Chemistry, 2005, 690(24-25): 5841-5848
[62] Noemi Cabello-Sanchez, Ludovic Jean, Jacques Maddaluno, Marie-Claire Lasne, and Jacques Rouden, Palladium-Mediated N-Arylation of Heterocyclic Diamines: Insights into the Origin of an Unusual Chemoselectivity. Journal of Organic Chemistry, 2007,72(6):2030-2039;
[63] Reddy Nagavelli Prabhakar and Tanaka Masato, Palladium-catalyzed amination of aryl chlorides. Tetrahedron Letters, 1997, 38(27): 4807-4810;
[64] Eric Brenner and Yves Fort, New efficient nickel(0) catalysed amination of aryl chlorides. Tetrahedron Letters, 1998, 39(30): 5359-5362;
[65] Eric Brenner, Rapha?l Schneider and Yves Fort, Nickel-catalysed couplings of aryl chlorides with secondary amines and piperazines. Tetrahedron, 1999, 55(44): 12829-12842;
[66] Benot Gradel, Eric Brenner, Rapha?l Schneider and Yves Fort, Nickel-catalysed amination of aryl chlorides using a dihydroimidazoline carbene ligand. Tetrahedron Letters, 2001, 42(33): 5689-5692;
[67] Matthias Beller, Claudia Breindl, Thomas H. Riermeier and Annegret Tillack, Synthesis of 2,3-Dihydroindoles, Indoles and Anilines by Transition Metal-Free Amination of Aryl Chlorides. Journal of Organic Chemistry, 2001, 66(4): 1403-1412;
[68] Y. Li George, Zheng Gang and F. Noonan Andrew, Highly Active, Air-Stable Versatile Palladium Catalysts for the C?C, C?N and C?S Bond Formations via Cross-Coupling Reactions of Aryl Chlorides. Journal of Organic Chemistry, 2001, 66(25): 8677-8681;
[69] R.Buchmeiser Michael,Thomas Schareina,Rhett Kempe and Klaus Wurst, Bis(pyrimidine)-based palladium catalysts: synthesis, X-ray structure and applications in Heck–, Suzuki–, Sonogashira–Hagihara couplings and amination reactions. Journal of Organometallic Chemistry, 2001, 634(1): 39-46;
[70] Andreas Ehrentraut, Alexander Zapf and Matthias Beller, A new improved catalystfor the palladium-catalyzed amination of aryl chlorides. Journal of Molecular Catalysis A: Chemical, 2002, 182-183: 515-523;
[71] Anil S. Gajare, Kozo Toyota, Masaaki Yoshifuji and Fumiyuki Ozawa, Application of a diphosphinidenecyclobutene ligand in the solvent-free copper-catalysed amination reactions of aryl halides. Chemical Communications (Cambridge, United Kingdom), 2004, 2004 (17):1994-1995;
[72] L. J. Goo?en, J. Paetzold, O. Briel, A. Rivas-Nass, R. Karch, B. Kayser, Buchwald-Hartwig Aminations of Aryl Chlorides:A Practical Protocol Based on Commercially Available Pd(0)-NHC Catalysts. Synlett, 2005, 2005(02): 275-278;
[73] Lange Ben de, H. Lambers-Verstappen Marielle, Lizette Schmieder-van de Vondervoort, Natascha Sereinig, Ron de Rijk, AndréH. M. de Vries, Johannes G. de Vries, Aromatic Amination of Aryl Bromides Catalysed by Copper/β-Diketone Catalysts:The Effect of Concentration. Synlett, 2006, 2006(18): 3105-3109;
[74] Chen Chen and Yang Lian-Ming, Ni(II)?(σ-Aryl) Complex:A Facile, Efficient Catalyst for Nickel-Catalyzed Carbon?Nitrogen Coupling Reactions. Journal of Organic Chemistry, 2007, 72(16): 6324-6327;
[75] Sasmita Tripathy, Richard LeBlanc, Tony Durst, Formation of 2-Substituted Iodobenzenes from Iodobenzene via Benzyne and Ate Complex Intermediates. Organic Letters, 1999, 1(12): 1973-1975;
[76] Kang Suk-Ku, Lee Sang-Ho, Lee Duckhee, Copper-Catalyzed N-Arylation of Amines with Hypervalent Iodonium Salts. Synlett, 2000, 2000 (07): 1022-1024;
[77] Kwong Fuk Yee, Klapars Artis, L. Buchwald Stephen, Copper-Catalyzed Coupling of Alkylamines and Aryl Iodides: An Efficient System Even in an Air Atmosphere. Organic Letters, 2002, 4(4): 581-584;
[78] Ma Dawei, Cai Qian, Zhang Hui, Mild Method for Ullmann Coupling Reaction of Amines and Aryl Halides. Organic Letters, 2003, 5(14): 2453-2455;
[79] Zhang Zhanjin, Mao Jincheng, Zhu Di,Wu Fan, Chen Huilin and Wan Boshun, Highly efficient copper-catalyzed N-arylation of alkylamines with aryl iodides using phosphoramidite as ligand. Catalysis Communications, 2005, 6(12): 784-787;
[80] Israel Conesa Lerma, Mark J. Cawley, F. Geoffrey N. Cloke, Katherine Arentsen, James S. Scott, Stuart E. Pearson, John Hayler and Stephen Caddick, Studies on Pd/imidazolium salt protocols for aminations of aryl bromides and iodides using lithium hexamethyldisilazide (LHMDS). Journal of Organometallic Chemistry, 2005, 690(24-25): 5841-5848;
[81] Zhang Hui, Cai Qian, Ma Dawei, Amino Acid Promoted CuI-Catalyzed C?N Bond Formation between Aryl Halides and Amines or N-Containing Heterocycles. Journal of Organic Chemistry, 2005, 70(13): 5164-5173;
[82] S.Yadav Lal Dhar, S.Yadav Beerendra, K.Rai Vijai, Active-Copper-Promoted Expeditious N-Arylations in Aqueous Media under Microwave Irradiation. Synthesis,2006, 2006 (11): 1868-1872;
[83] Zhang Zhanjin, Mao Jincheng, Zhu Di, Wu Fan, Chen Huilin and Wan Boshun, Highly efficient and practical phosphoramidite–copper catalysts for amination of aryl iodides and heteroaryl bromides with alkylamines and N(H)-heterocycles. Tetrahedron, 2006, 62(18): 4435-4443;
[84] Zhu Di, Wang Rongliang, Mao Jincheng, Xu Lei, Wu Fan and Wan Boshun, Efficient copper-catalyzed amination of aryl halides with amines and N-H heterocycles using rac-BINOL as ligand. Journal of Molecular Catalysis A: Chemical, 2006, 256(1-2): 256-260;
[85] Yang Minghua and Liu Fei, An Ullmann Coupling of Aryl Iodides and Amines Using an Air-Stable Diazaphospholane Ligand. Journal of Organic Chemistry, 2007, 72(23): 8969-8971;
[86] Laxmidhar Rout, Suribabu Jammi, T. Punniyamurthy, Novel CuO Nanoparticle Catalyzed C?N Cross Coupling of Amines with Iodobenzene. Organic Letters, 2007, 9(17): 3397-3399;
[87] Guo Diliang, Huang He, Xu Jinyi, Jiang Hualiang and Liu Hong, Efficient Iron-Catalyzed N-Arylation of Aryl Halides with Amines. Organic Letters, 2008, 10(20): 4513-4516;
[88] Wittig and Merkle, Ber., 1943, 76, 109
[89] Le Fevre, Preparatin and Dinitration of 1-Phenylpiperidine. J.Chem.Soc.,1932, 1376-1379
[90] R. Katritzky Alan, Fan Weiqiang, The chemistry of benzotriazole.A novel and versatile synthesis of 1-alkyl-, 1-aryl-, 1-(alkylamino)-, or 1-amido-substituted and of 1,2,6-trisubstituted piperidines from glutaraldehyde and primary amines or monosubstituted hydrazines. Journal of Organic Chemistry, 1990, 55(10): 3205-3209;
[91] M. Berman Ashley, S. Johnson Jeffrey, Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents. Journal of the American Chemical Society, 2004, 126(18): 5680-5681;
[92] M. Berman Ashley, M. Berman Jeffrey, Nickel-Catalyzed Electrophilic Amination of Organozinc Halides. Synlett, 2005, 2005 (11): 1799-1801;
[93] M. Berman Ashley, S. Johnson Jeffrey, Copper-Catalyzed Electrophilic Amination of Organozinc Nucleophiles: Documentation of O-Benzoyl Hydroxylamines as Broadly Useful R2N(+) and RHN(+) Synthons. Journal of Organic Chemistry, 2006, 71(1): 219-224;
[94] J.Campbell Matthew, S.Johnson Jeffrey, Mechanistic Studies of the Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents and Development of a Zinc-Free Protocol. Organic Letters, 2007, 9(8): 1521-1524;
[95] Ishikawa Teruhiko, Uedo Eiji, Tani Rie and Saito Seiki, Aromatization of Enamines Promoted by a Stoichiometric Amount of Palladium(II) Salts: A Novel Method for theSynthesis of Aromatic Amines. Journal of Organic Chemistry, 2001, 66(1): 186-191
[96] Srinivas Gadthula, Periasamy Mariappan, Aromatization of enamines using the TiCl4/Et3N reagent system. Tetrahedron Letters, 2002, 43(15): 2785-2788
[97] D. Quach Tan, A. Batey Robert, Ligand- and Base-Free Copper(II)-Catalyzed C?N Bond Formation:Cross-Coupling Reactions of Organoboron Compounds with Aliphatic Amines and Anilines. Organic Letters, 2003, 5(23): 4397-4400
[98] M. Lakshmi Kantam, B. Neelima, Ch. Venkat Reddy and V. Neeraja, N-Arylation of imidazoles, imides, amines, amides and sulfonamides with boronic acids using a recyclable Cu(OAc)2·H2O/[bmim][BF4] system. Journal of Molecular Catalysis A: Chemical, 2006, 249(1-2): 201-206;
[99] Sreedhar Bojja, T.Venkanna Gopaladasu, Kota Balaji Shiva Kumar, Vura Balasubrahmanyam, Copper(I) Oxide Catalyzed N-Arylation of Azoles and Amines with Arylboronic Acid at Room Temperature under Base-Free Conditions. Synthesis, 2008, 2008(05): 795-799;
[100] Xu Gang, Wang Yan-Guang, Microwave-Assisted Amination from Aryl Triflates without Base and Catalyst. Organic Letters, 2004, 6(6): 985-987
[101] Gao Cai-Yan, Yang Lian-Ming, Nickel-Catalyzed Amination of Aryl Tosylates. Journal of Organic Chemistry, 2008, 73(4): 1624-1627;
[102] M. Berman Ashley, S. Johnson Jeffrey, Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents. Journal of the American Chemical Society, 2004, 126(18): 5680-5681;
[103] M. Berman Ashley, S. Johnson Jeffrey, Copper-Catalyzed Electrophilic Amination of Organozinc Nucleophiles: Documentation of O-Benzoyl Hydroxylamines as Broadly Useful R2N(+) and RHN(+) Synthons. Journal of Organic Chemistry, 2006, 71(1): 219-224
[104] A. Miller Joseph, W. Dankwardt John, M. Penney Jonathan, Nickel Catalyzed Cross-Coupling and Amination Reactions of Aryl Nitriles. Synthesis, 2003, 2003 (11): 1643-1648;
[105] Christophe Desmarets, Rapha?l Schneider, Yves Fort, Nickel-mediated amination chemistry. Part 1: Efficient aminations of (het)aryl 1,3-di and 1,3,5-trichlorides. Tetrahedron Letters, 2000, 41(16): 2875-2879;
[106] P. Beletskaya Irina, G..Bessmertnykh Alla, Roger Guilard, Palladium-catalyzed amination of aryl dibromides with secondary amines: synthetic and mechanistic aspects. Tetrahedron Letters, 1999, 40(35): 6393-6397;
[107] H. R. Barton Derek, Finet Jean-Pierre, Khamsi Jamal, Copper salts catalysis of N-phenylation of amines by trivalent organobismuth compounds. Tetrahedron Letters, 1987, 28(8): 887-90;
[108] Sakurai, Bull.Chem.Soc. Japan, 1938, 13(7): 482-488
[109] L. Romera Juan, M. Cid José, A. Trabanco Andrés, Potassium iodide catalysedmonoalkylation of anilines under microwave irradiation. Tetrahedron Letters, 2004, 45: 8797–8800
[110] Ju Yuhong,S. Varma Rajender, An Efficient and Simple Aqueous N-Heterocyclization of Aniline Derivatives: Microwave-Assisted Synthesis of N-Aryl Azacycloalkanes. Org. Lett., 2005, 7(12): 2409-2411
[111] Ju Yuhong,S. Varma Rajender, Aqueous N-Heterocyclization of Primary Amines and Hydrazineswith Dihalides: Microwave-Assisted Syntheses of N-Azacycloalkanes, Isoindole, Pyrazole, Pyrazolidine and Phthalazine Derivatives. J. Org. Chem., 2006, 71(1): 135-141
[112] T. Michael Barnard, Grace S. Vanier, Michael J. Collins, Scale-Up of the Green Synthesis of Azacycloalkanes and Isoindolines under Microwave Irradiation. Organic Process Research & Development, 2006, 10(6): 1233-1237
[113] Periasamy Mariappan, K. Jayakumar Natarajan, Bharathi Pandi, Aryltitanium Species through the Reaction of N,N-Dialkylarylamines with TiCl4: Oxidative Coupling, N-Dealkylation, and Reaction with Electrophiles. Journal of Organic Chemistry, 2000, 65(11): 3548-3550
[114] B.Singh Chingakham, Kavala Veerababurao, K.Samal Akshaya, Patel Bhisma K., Aqueous-Mediated N-Alkylation of Amines. European Journal of Organic Chemistry, 2007, 2007 (8): 1369-1377
[115] A. N. Bourns, 1-PHENYLPIPERIDINE. Organic Syntheses, Coll. 1963, 4: 795; 1954, 34, 79
[116] Robert E.Walkup, Searles Scott, Synthesis of sterically hindered 1-arylpyrrolidines and 1-arylpiperidines by condensation of primary aromatic amines with cyclic ethers or diols. Tetrahedron, 1985, 41(1): 101-106
[117] S. Gajare Anil, Kozo Toyota, Masaaki Yoshifuji, Fumiyuki Ozawa, Solvent Free Amination Reactions of Aryl Bromides at Room Temperature Catalyzed by a (π-Allyl) palladium Complex Bearing a Diphosphinidenecyclobutene Ligand. Journal of Organic Chemistry, 2004, 69(19): 6504-6506
[118] Y. Watanabe, S.C.Shim, T. Mitaudo, M.Yamashita, Y. Takegami, The Facile Synthesis of N-Substituted piperidines from Glutaraldehyde and Primary Amines with Tetracarbonylhydridoferrate. Bull. Chem. Soc. Jpn., 1976, 49(8): 2302-2305
[119] Verardo Giancarlo,Dolce Anna ,Toniutti Nicoletta,Reductive One Batch Synthesis of N-Substituted Pyrrolidines from Primary Amines and 2,5-Dimethoxytetrahydrofuran. Synthesis, 1999, 1999(01): 74-79
[120] R.Katritzky Alan, Fan Weiqiang, The chemistry of benzotriazole. A novel and versatile synthesis of 1-alkyl-, 1-aryl-, 1-(alkylamino)-, or 1-amido-substituted and of 1,2,6-trisubstituted piperidines from glutaraldehyde and primary amines or monosubstituted hydrazines. Journal of Organic Chemistry, 1990, 55(10): 3205-3209
[121] Suwa Toshihiro, Sugiyama Erika, Shibata Ikuya, Baba Akio, ChemoselectiveReductive Amination of Aldehydes and Ketones by Dibutylchlorotin Hydride-HMPA Complex. Synthesis, 2000, 2000 (06): 789-800
[122] Verardo Giancarlo, Angelo G. Giumanini, Favret Grazia, Strazzolini Paolo, Reductive One Batch Synthesis of N-Arylpiperidines From Primary Amines and Glutaraldehyde. Synthesis, 1991, 1991(06): 447-450;
[123] Reynolds and Kenyon, J.Am.Chem.Soc., 1950, 72: 1597-1598
[124] Tsuji Yasushi, Huh Keun-Tae, Ohsugi Yukihiro, Watanabe Yoshihisa, Ruthenium Complex Catalyzed N-Heterocyclization. Syntheses of N-Substituted Piperidines, Morpholines, and Piperazines from Amines and 1,5-Diols. J. Org. Chem., 1985, 50(9): 1365-1370
[125] K.Felf?ldi, M.S. Klyavlin and M.Bartók, Transformation of organic compounds in the presence of metal complexes V*. Cyclization of aminoalcohols on a ruthenium complex. Journal of Organometallic Chemistry, 1989, 362(1-2): 193-195
[126] RobA.T.M.Abbenhuis,Jaap.Boersma,Gerard.van,Koten,Ruthenium-Complex-Catalyzed N-(Cyclo)alkylation of Aromatic Amines with Diols. Selective Synthesis of N-(ω-Hydroxyalkyl) anilines of Type PhNH(CH2)nOH and of Some Bioactive Arylpiperazines. J. Org. Chem., 1998, 63(13): 4282-4290
[127] S.A.Hamid Malai Haniti, M.J.Williams Jonathan, Ruthenium catalysed N-alkylation of amines with alcohols, Chem. Commun, 2007: 725–727
[128] G . Ecke George, P. Napolitano John, H. Filbey Allen, ortho-Alkylation of Aromatic Amines. J.Org.Chem., 1957, 22: 639-642
[129] Frédéric Valot, Fabienne Fache, Roland Jacquot, Michel Spagnol and Marc Lemaire, Gas-phase selective N-alkylation of amines with alcohols overγ-alumina. Tetrahedron Letters, 1999, 40: 3689-3592
[130] Sankarasubbier Narayanan, Kiranmayi Deshpande, Aniline alkylation over solid acid catalysts. Applied Catalysis A: General, 2000, 199: 1–31
[131] D.Yadav Ganapati, S.Doshi Nirav, Alkylation of aniline with methyl-tert-butyl ether (MTBE) and tert-butanol over solid acids: product distribution and kinetics. Journal of Molecular Catalysis A: Chemical, 2003, 194: 195–209
[132] Yur’ev, Yu. K, Prokina.M.N., J.Gen.Chem.USSR 7, 1938,1868; Chem.Abstr., 1938, 32: 548
[133] Charles A. Bordner, Charles G. Karmin, Niagara Falls., Production of pyrrolidine. [P]US:2525584, 1950, 10: 10
[134] L.Meszaros. et al, Acta Univ. Szegedienesis Acta Phys. et Chem.[N.S.], 1958, 4: 144-152
[135] H.Vaserrnans, S.Hillers, A.Avots, The preparation of new ganglion-blocking agents“pentapyrrolidine”and“tetrapiperdine”[J], Latvijas PSP Zinatnu Akad. Vestis., 1958, 5: 79-86
[136] Fujita K, Hatada K, Ono Y. et al, Ring transformation of tetrahydrofuran intopyrrolidine over synthetic zeolite[J]. J.Catal., 1974, 35: 325
[137] Kou Hatada, Massatoshi Shimada, Katsuhiro Fujita, et al., Ring transformations of oxygen containing heterocycles into nitrogen containing heterocycles over synthetic zeolites[J]. Chem Lett, 1974: 439-442
[138] Yoshio Ono, Kou Hatada, Katsuhiro Fujita, et al., Type L zeolites as selective catalysts for the ring transformation of cylic ethers into cyclic lmines[J]. J.Catal., 1976, 41: 322
[139] Nomura M, Tomogane T, Kikkawa S, et al., Exchange reaction of tetrahydrofuran to pyrrolidine with ammonia over supported transition metalchloride catalysts[J]. Sekiyu Gakkai Shi, 1977, 20(5): 419-422
[140] Iwasaki Mineyuki, Production of parrolidine [P]. JP:1268681, 1989, 10: 26
[141] An Nan Ko, Ching ling Yang, Applied Catalysis A:General, 1996, 134: 53-56
[142]甄开吉等主编,催化作用基础.北京:科学出版社,2005.284~288
[143]黄仲涛主编,工业催化.北京:化学工业出版社,1994. 99
[144]王桂茹主编,催化剂与催化作用.大连.大连理工大学出版社,2000. 324
[145]高正中编,实用催化.北京:化学工业出版社,1996. 191~192