硅胶嫁接聚丙烯酸固载DMAP催化剂的合成及其催化性能研究
|
摘要
本文设计了一种以硅胶嫁接丙烯酸做为载体固载的DMAP催化剂S-PAA-DMAP。其合成路线以吡啶为原料,首先将吡啶通过氧化,硝化得到N-氧化硝基吡啶2,还原后得到4-氨基吡啶3,再与两分子丙烯酸甲酯通过迈克尔加成得到化合物4,再在甲苯中通过强碱甲醇钠的作用发生克莱森酯缩合,然后在20%盐酸作用下脱羧得到1-吡啶基-4-哌啶酮,再在50%的乙醇溶液中与盐酸羟胺生成肟5,再在甲醇中以雷内镍作催化剂加氢还原得到6,在与Boc保护的6-氨基己酸反应后得到化合物7,经脱保护后得到末端带有氨基的DMAP类似物8。将DMAP类似物8与硅胶嫁接丙烯酸连接后得到了我们设计的催化剂S-PAA-DMAP。
在催化实验部分我们用设计合成的催化剂S-PAA-DMAP催化了环己二酮衍生物的Fries重排反应和α-苯乙醇的乙酰化反应都得到了较好的效果。在Fries重排实验中我们用了底物30%mol的催化剂反应6~8h即可使原料转化完全。苯乙醇的乙酰化反应中使用10mol%的S-PAA-DMAP能够达到与DMAP相近的效果,催化剂重复利用五次分别得到了91%,88%,84%,82%及82%的产率,表明了S-PAA-DMAP具有良好的催化稳定性。
Polymer catalysts are referring to all of the polymer materials with catalytic activities in chemical reactions,which is an important branch of functional polymer materials. By the inspiration of Merrifield solid phase synthesis,the organic polymers (polystyrene sulfuric acid) loading ([Pt (NH3)4 ]2+) complex catalyst finally came out . This research work immediately sparked widespread concern and interest of catalytic scientists around the world, since then Polymer-supported catalytic complex catalysis has become an independent field of cross-disciplinary research. In the subsequent 30 years people have designed and synthesized a large number of Polymer-supported catalysts with different structures and different uses, and due to the polymer effect among the various functional groups in the polymer chain, such as synergy, some have special optically active structures, and their catalytic activity in selective catalysis were much higher than the corresponding homogeneous small molecules catalyst.
In a large number of small-molecule catalysts ,4-N, N dimethylamino-pyridine (DMAP), due to its strong nucleophilicity is often used as a catalyst for a number of important reactions, such as acylation, silylation, triphenyl methylation, and ester rearrangement, Darkin-West reaction, Baylis-Hillman reaction. However, because of its belonging to small organic molecules, DMAP does not facilitate the recovery and utilization, resulting in wasted costs. In order to change this situation many researchers have grafted it to low-cost commercial materials, such as organic polymer resins, inorganic materials (silica gel and molecular sieve), and micro-capsules. We found that either the soluble homogeneous catalysts or the insoluble heterogeneous catalysts had more or less deficiencies when they were recycled. By comparing a variety of supported DMAP catalysts in the literature, we designed to combine the single soluble homogeneous catalysts and the insoluble heterogeneous catalysts, based on such considerations we have chosen silica gel grafted polyacrylic acid, which is a combination of silica gel and polyacrylic acid, as the carrier to immobilize DMAP. This carrier will set the advantages of organic polymer and silica gel in one: the linear long chain polyacrylic acid polymer is soluble in a variety of solvents, and can extend freely in the reaction solvent system, so the catalyst can be fully utilized. While the silica is insoluble, so the silica supported catalyst can be filtered directly when the reaction is completed, and can be facilitate recycled. We use the coupling agentγ-amino propyltriethoxysilane to graft silica gel and polyacrylic acid polymer in our design. This design combines the advantages of both while cleverly avoiding its shortcomings.
In this paper, we designed to use pyridine as the raw materials. First we got nitropyridine N-oxide 2 through the oxidation and nitration, after reduction we got 4-aminopyridine 3, which then reacted with two molecules of methyl acrylate through the Michael addition to generate compound 4. 1-pyridyl-4-piperidine-one was synthesized via Claisen ester condensation and decarboxylation from 4, and then reacted with hydroxylamine hydrochloride in 50% ethanol solution to generate oxime 5. Compound 6 was obtained by hydrogenation in methanol using Raney nickel as the catalyst, which reacted with Boc-protected 6-aminocaproic acid to generate compound 7, the amino-terminal with DMAP analogue 8 was obtained by deprotection. S-PAA-DMAP was finally synthesized by connecting the DMAP analogue 8 and silica gel grafting polyacrylic acid.
To study the catalytic performance of S-PAA-DMAP catalyst, we chose Fries rearrangement and the acetylation ofα-phenylethanol as our model reaction in the catalytic part of our experiment. In Fries rearrangement we used 30% mol catalyst for reaction 6~8h to make raw materials completely transformed. Inα-Phenylethanol acetylation we used 10% mol both of S-PAA-DMAP and DMAP to achieve similar results. The catalyst was reused three times, to get a result respectively, 91%, 86% and 84% in yield. S-PAA-DMAP has a good stability as a catalyst, which put forward a new mode of thinking for the future work of the immobilized catalyst.
在催化实验部分我们用设计合成的催化剂S-PAA-DMAP催化了环己二酮衍生物的Fries重排反应和α-苯乙醇的乙酰化反应都得到了较好的效果。在Fries重排实验中我们用了底物30%mol的催化剂反应6~8h即可使原料转化完全。苯乙醇的乙酰化反应中使用10mol%的S-PAA-DMAP能够达到与DMAP相近的效果,催化剂重复利用五次分别得到了91%,88%,84%,82%及82%的产率,表明了S-PAA-DMAP具有良好的催化稳定性。
Polymer catalysts are referring to all of the polymer materials with catalytic activities in chemical reactions,which is an important branch of functional polymer materials. By the inspiration of Merrifield solid phase synthesis,the organic polymers (polystyrene sulfuric acid) loading ([Pt (NH3)4 ]2+) complex catalyst finally came out . This research work immediately sparked widespread concern and interest of catalytic scientists around the world, since then Polymer-supported catalytic complex catalysis has become an independent field of cross-disciplinary research. In the subsequent 30 years people have designed and synthesized a large number of Polymer-supported catalysts with different structures and different uses, and due to the polymer effect among the various functional groups in the polymer chain, such as synergy, some have special optically active structures, and their catalytic activity in selective catalysis were much higher than the corresponding homogeneous small molecules catalyst.
In a large number of small-molecule catalysts ,4-N, N dimethylamino-pyridine (DMAP), due to its strong nucleophilicity is often used as a catalyst for a number of important reactions, such as acylation, silylation, triphenyl methylation, and ester rearrangement, Darkin-West reaction, Baylis-Hillman reaction. However, because of its belonging to small organic molecules, DMAP does not facilitate the recovery and utilization, resulting in wasted costs. In order to change this situation many researchers have grafted it to low-cost commercial materials, such as organic polymer resins, inorganic materials (silica gel and molecular sieve), and micro-capsules. We found that either the soluble homogeneous catalysts or the insoluble heterogeneous catalysts had more or less deficiencies when they were recycled. By comparing a variety of supported DMAP catalysts in the literature, we designed to combine the single soluble homogeneous catalysts and the insoluble heterogeneous catalysts, based on such considerations we have chosen silica gel grafted polyacrylic acid, which is a combination of silica gel and polyacrylic acid, as the carrier to immobilize DMAP. This carrier will set the advantages of organic polymer and silica gel in one: the linear long chain polyacrylic acid polymer is soluble in a variety of solvents, and can extend freely in the reaction solvent system, so the catalyst can be fully utilized. While the silica is insoluble, so the silica supported catalyst can be filtered directly when the reaction is completed, and can be facilitate recycled. We use the coupling agentγ-amino propyltriethoxysilane to graft silica gel and polyacrylic acid polymer in our design. This design combines the advantages of both while cleverly avoiding its shortcomings.
In this paper, we designed to use pyridine as the raw materials. First we got nitropyridine N-oxide 2 through the oxidation and nitration, after reduction we got 4-aminopyridine 3, which then reacted with two molecules of methyl acrylate through the Michael addition to generate compound 4. 1-pyridyl-4-piperidine-one was synthesized via Claisen ester condensation and decarboxylation from 4, and then reacted with hydroxylamine hydrochloride in 50% ethanol solution to generate oxime 5. Compound 6 was obtained by hydrogenation in methanol using Raney nickel as the catalyst, which reacted with Boc-protected 6-aminocaproic acid to generate compound 7, the amino-terminal with DMAP analogue 8 was obtained by deprotection. S-PAA-DMAP was finally synthesized by connecting the DMAP analogue 8 and silica gel grafting polyacrylic acid.
To study the catalytic performance of S-PAA-DMAP catalyst, we chose Fries rearrangement and the acetylation ofα-phenylethanol as our model reaction in the catalytic part of our experiment. In Fries rearrangement we used 30% mol catalyst for reaction 6~8h to make raw materials completely transformed. Inα-Phenylethanol acetylation we used 10% mol both of S-PAA-DMAP and DMAP to achieve similar results. The catalyst was reused three times, to get a result respectively, 91%, 86% and 84% in yield. S-PAA-DMAP has a good stability as a catalyst, which put forward a new mode of thinking for the future work of the immobilized catalyst.
引文
[1]陈义镛,功能高分子,上海科学技术出版社,1988,5
[2]马建标,功能高分子材料,化学工业出版社,2000,7
[3] Astle M J,Schaeffer B,Obenland C O. Esterification of Glycols by Acids in the Presence of Cation Exchange Resins [J].J.Am.Chem.Soc.,1955,77:3643
[4] Grubbs R H. et al.,Catalytic reduction of olefins with a polymer-supported rhodium (I) catalyst [J].J.Am.Chem.Soc.,1971,93,3062
[5] Grubbs R H. et al.,J.Macromol.Sci.Chem.,A7,1973,1047
[6]钱宝庭,离子交换剂应用技术,天津科学技术出版社,1984,12
[7] Chem.Abstr.,68,68325u (1968)
[8] Steglich W,Hofle G,Angew.Chem.Int.Ed.Engl.,1969,8,981
[9]廖联安,郭奇玲。4-二甲氨基吡啶的合成及其催化的有机反应[J].合成化学, 1995,3 (3):215
[10] G. Steglich H, W and Vorbruggen H, [J].Angew. Chem., lnt. Ed. Engl.,1978, 17,569
[11] Michael A. Hierl, Edward P. Gamson, and Irving M. Klotz ,Nucleophilic Catalysis by Polyethylenimines with Covalently Attached 4-Dialkylaminopyridine [J].J. Am. Chem. SOC.,1979, 101:6020
[12]曾文平,段湘生,聂萍。4-二甲氨基吡啶的合成及应用[J].精细化工中间体, 2001,31(5) :5.
[13] Ziegler F E,Berger G D [J].Synth.Commun.,1979,539
[14] Weinhouse M I,Janda K D [J].Synthesis,1993,(1),81
[15] Douglass F. Taber, John C. Amedio Jr., and Yogesh K. Patel Preparation of .beta.-keto esters by 4-DMAP-catalyzed ester exchange [J]. J. Org. Chem., 1985, 50 (19):3618-3619
[16] Douglass F. Taber, P. Bruce Deker, and Micheal D. Gaul Enantioselective construction of dialkylcarbinols:synthesis of (-)-5-hexadecanolide [J]. J. Am.Chem. Soc., 1987, 109 (24): 7488-7494
[17] Hatakeyama, S.;Satoh,K.;Takano,S.;Efficient ester exchange reaction of phosphonoacetates [J].Tetrahedron Lett., 1987,28:2713-2716
[18] Hoofle G,Prox A,Steglich W [J].Chem.Ber.,1972,105,1718
[19] Lepachy J, Hoofle G,Wilschowitz L,Steglich W [J].Ann.Chem.,19741753
[20] Chaudhary S K , A simplified procedure for the preparation of triphenylmethylethers [J]. Tetrahedron Lett. , 1979, 2:95.
[21] Pankiewicz K W, Krzeminski J., and Watanabe K. A. Synthesis of 2'-.beta.-fluoro- and 3'-.alpha.-fluoro-substituted guanine nucleosides. Effect of sugar conformational shifts on nucleophilic displacement of the 2'-hydroxy and 3'-hydroxy group with DAST [J]. J. Org. Chem., 1992, 57 (26):7315-7321
[22] Merger F,Towae F,Schroff L;US 4 192 94,1980
[23] Bosch I, Romea P, UrpíF, Vilarrasa J, Alternative procedures for the macrolactamisation ofω-Azido Acids [J].Tetrahedron Lett., 1993,34(32): 4671-4674
[24] Molina P, Alajarín M, Sánchez-Andrada P Medium- and large-membered rings from bis(iminophosphoranes): An efficient preparation of cyclic carbodiimides [J].Tetrahedron Lett., 1993,34(32):5155-5158
[25] Bergbreiter D E and Chunmei Li Poly (4-tert-butylstyrene) as a Soluble Polymer Support in Homogeneous Catalysis [J]. Org. Lett.,2003,5 (14):2445-2447)
[26] Bergbreiter D E., Osburn P L, Smith T, Chunmei Li, and Frels J D Using Soluble Polymers in Latent Biphasic Systems [J].J. AM. CHEM. SOC. 2003, 125, 6254-6260
[27] David E. Bergbreiter, Philip L. Osburn, and Chunmei Li Soluble Polymer-Supported Catalysts Containing Azo Dyes [J]. Org. Lett.,2002, 4(5):737-740
[28] JITAO HUANG,QIANG WANG,JINKUN YAO,LIMING ZHANG,JINGWU SUN Synthesis and Chemical Modification of New Epoxy Resins Containing Alkylaminopyridines [J]. Journal of Applied Polymer Science,1999,71:1101–1105
[29] Hung-Ting Chen,Huh S.,Wiench J. W.,Pruski M. and ictor S.-Y. Lin, Dialkylaminopyridine-Functionalized Mesoporous Silica Nanosphere as an Efficient and Highly Stable Heterogeneous Nucleophilic Catalyst [J]. J. AM. CHEM. SOC. 2005,127:13305-13311
[30] Rubinsztajn, S.; Zeldin, M.; Fife, W. K. New Transacylation Catalysts: Silanes and Siloxanes Functionalized with 4-(Dialky1amino) pyridine Moieties [J].Macromolecules 1990, 23:4026-4027
[31] Rubinsztajn S., Zeldin M., and Fife W. K. Synthesis, Characterization, and Solubility Behavior of Polysiloxanes with 4-(Dialky1amino) pyridine Functions [J].Macromolecules 1991, 24:2682-2688
[32] Price K. E.,Mason B. P., Bogdan A. R.,Broadwater S. J.,Steinbacher J.L.,and McQuade D. T. Microencapsulated Linear Polymers:“Soluble”Heterogeneous Catalysts [J]. J. AM. CHEM. SOC. 2006,128:10376-10377
[33] Mason B. P., Bogdan A. R., Goswami A., and McQuade D. T. A General Approach to Creating Soluble Catalytic Polymers Heterogenized in Microcapsules [J]. Org. Lett.,2007,9( 17):3449-3451
[34] Deratani, A.; Darling, G. D.; Horak, D.; Frechet, J. M.Heterocyclic Polymers as Catalysts in Organic Synthesis. Effect of Macromolecular Design and Microenvironment on the Catalytic Activity of Polymer-Supported (Dialky1amino)pyridine Catalysts[J]. Macromolecules1987, 20:767-772
[35] Menger, F. M.; McCann, D. J. A Polymer-Bound 4-Aminopyridine: Synthesis and Reactivity [J].J. Org. Chem. 1985, 50:3928-3930
[36]黄积涛孙经武曹爱丽张嘉琪高分子酰化催化剂聚4-3-吡咯啉基吡啶的合成[J].化学世界, 1996, 7:367-370
[37] Mammen M, Dahmann G, and George M, Whitesides Effective Inhibitors of Hemagglutination by Influenza Virus Synthesized from Polymers HavingActive Ester Groups.[J].J. Med. Chem., 1995, 38 (21):4179-4190
[38] Pollak A; Blumenfeld H; Wax M; Baughn R L; Whitesides G M Enzvme Immobilization bv Condensation Copolvmerization into cross-Linked Polyacryiamide Gels. [J].J.Am.Chem.SOC.1980, 102:6324-6336
[39] Weitkamp J, Hunger M, Rymsa U Base catalysis on microporous and mesoporous materials: recent progress and perspectives [J]. Microporous and Mesoporous Materials 2001, 48:255-270
[40] Cauvel A, Renard G, Brunel D Monoglyceride Synthesis by Heterogeneous Catalysis Using MCM-41 Type Silicas Functionalized with Amino Groups [J].J. Org. Chem. 1997, 62:749-751
[41] ZHANG Xue-Hong, CHEN Bing, WEI Wei, SUN Yu-Han Preparation of Functionalized Porous Silica by Ultrasonic Technique for the Methylation Reaction of Phenol with Dimethyl Carbonate [J]. Chinese Journal of Chemistry 2005 23 (10): 1376-1380
[42] Ochiai E Recent Japanese work on the chemistry of pyridine 1-oxide and related compounds [J]. J Org Chem., 1953, 18:534-551。
[43]朱秋华,陈卫民4-硝基吡啶N-氧化物制备方法的改进[J].中国医药工业杂志, 2000,31 (2):556- 557.
[44]任勇,刘静. 4-氨基吡啶的合成[J].化学试剂, 1998 , 20(4):240- 241.
[45]王志祥,张志炳. 4-氨基吡啶合成的改进[J].中国医药工业杂志, 2001, 32 (2):83- 84.
[46]张红艳,刘尚远,赵增国N -氧化-4-硝基吡啶的合成及表征[J].天津师范大学学报(自然科学版),2004,24(4):12-13.
[47]杨春常,范平,黄治清,等.对氨基吡啶的合成与研究[J].辽宁化工, 1991, 28 (3): 36237.
[48] Edward J, Delaney, Wood L E, Irving M Klotz Poly(ethylenimines) with Alternative (Alky1amino)pyridines as Nucleophilic Catalysts [J].J. Am. Chem. SOC. 1982,104:799-807
[49]李乐平段学民陈立功N-烷基-3-吡咯酮类化合物的合成[J].精细化工,2005,22(2):158-160
[2]马建标,功能高分子材料,化学工业出版社,2000,7
[3] Astle M J,Schaeffer B,Obenland C O. Esterification of Glycols by Acids in the Presence of Cation Exchange Resins [J].J.Am.Chem.Soc.,1955,77:3643
[4] Grubbs R H. et al.,Catalytic reduction of olefins with a polymer-supported rhodium (I) catalyst [J].J.Am.Chem.Soc.,1971,93,3062
[5] Grubbs R H. et al.,J.Macromol.Sci.Chem.,A7,1973,1047
[6]钱宝庭,离子交换剂应用技术,天津科学技术出版社,1984,12
[7] Chem.Abstr.,68,68325u (1968)
[8] Steglich W,Hofle G,Angew.Chem.Int.Ed.Engl.,1969,8,981
[9]廖联安,郭奇玲。4-二甲氨基吡啶的合成及其催化的有机反应[J].合成化学, 1995,3 (3):215
[10] G. Steglich H, W and Vorbruggen H, [J].Angew. Chem., lnt. Ed. Engl.,1978, 17,569
[11] Michael A. Hierl, Edward P. Gamson, and Irving M. Klotz ,Nucleophilic Catalysis by Polyethylenimines with Covalently Attached 4-Dialkylaminopyridine [J].J. Am. Chem. SOC.,1979, 101:6020
[12]曾文平,段湘生,聂萍。4-二甲氨基吡啶的合成及应用[J].精细化工中间体, 2001,31(5) :5.
[13] Ziegler F E,Berger G D [J].Synth.Commun.,1979,539
[14] Weinhouse M I,Janda K D [J].Synthesis,1993,(1),81
[15] Douglass F. Taber, John C. Amedio Jr., and Yogesh K. Patel Preparation of .beta.-keto esters by 4-DMAP-catalyzed ester exchange [J]. J. Org. Chem., 1985, 50 (19):3618-3619
[16] Douglass F. Taber, P. Bruce Deker, and Micheal D. Gaul Enantioselective construction of dialkylcarbinols:synthesis of (-)-5-hexadecanolide [J]. J. Am.Chem. Soc., 1987, 109 (24): 7488-7494
[17] Hatakeyama, S.;Satoh,K.;Takano,S.;Efficient ester exchange reaction of phosphonoacetates [J].Tetrahedron Lett., 1987,28:2713-2716
[18] Hoofle G,Prox A,Steglich W [J].Chem.Ber.,1972,105,1718
[19] Lepachy J, Hoofle G,Wilschowitz L,Steglich W [J].Ann.Chem.,19741753
[20] Chaudhary S K , A simplified procedure for the preparation of triphenylmethylethers [J]. Tetrahedron Lett. , 1979, 2:95.
[21] Pankiewicz K W, Krzeminski J., and Watanabe K. A. Synthesis of 2'-.beta.-fluoro- and 3'-.alpha.-fluoro-substituted guanine nucleosides. Effect of sugar conformational shifts on nucleophilic displacement of the 2'-hydroxy and 3'-hydroxy group with DAST [J]. J. Org. Chem., 1992, 57 (26):7315-7321
[22] Merger F,Towae F,Schroff L;US 4 192 94,1980
[23] Bosch I, Romea P, UrpíF, Vilarrasa J, Alternative procedures for the macrolactamisation ofω-Azido Acids [J].Tetrahedron Lett., 1993,34(32): 4671-4674
[24] Molina P, Alajarín M, Sánchez-Andrada P Medium- and large-membered rings from bis(iminophosphoranes): An efficient preparation of cyclic carbodiimides [J].Tetrahedron Lett., 1993,34(32):5155-5158
[25] Bergbreiter D E and Chunmei Li Poly (4-tert-butylstyrene) as a Soluble Polymer Support in Homogeneous Catalysis [J]. Org. Lett.,2003,5 (14):2445-2447)
[26] Bergbreiter D E., Osburn P L, Smith T, Chunmei Li, and Frels J D Using Soluble Polymers in Latent Biphasic Systems [J].J. AM. CHEM. SOC. 2003, 125, 6254-6260
[27] David E. Bergbreiter, Philip L. Osburn, and Chunmei Li Soluble Polymer-Supported Catalysts Containing Azo Dyes [J]. Org. Lett.,2002, 4(5):737-740
[28] JITAO HUANG,QIANG WANG,JINKUN YAO,LIMING ZHANG,JINGWU SUN Synthesis and Chemical Modification of New Epoxy Resins Containing Alkylaminopyridines [J]. Journal of Applied Polymer Science,1999,71:1101–1105
[29] Hung-Ting Chen,Huh S.,Wiench J. W.,Pruski M. and ictor S.-Y. Lin, Dialkylaminopyridine-Functionalized Mesoporous Silica Nanosphere as an Efficient and Highly Stable Heterogeneous Nucleophilic Catalyst [J]. J. AM. CHEM. SOC. 2005,127:13305-13311
[30] Rubinsztajn, S.; Zeldin, M.; Fife, W. K. New Transacylation Catalysts: Silanes and Siloxanes Functionalized with 4-(Dialky1amino) pyridine Moieties [J].Macromolecules 1990, 23:4026-4027
[31] Rubinsztajn S., Zeldin M., and Fife W. K. Synthesis, Characterization, and Solubility Behavior of Polysiloxanes with 4-(Dialky1amino) pyridine Functions [J].Macromolecules 1991, 24:2682-2688
[32] Price K. E.,Mason B. P., Bogdan A. R.,Broadwater S. J.,Steinbacher J.L.,and McQuade D. T. Microencapsulated Linear Polymers:“Soluble”Heterogeneous Catalysts [J]. J. AM. CHEM. SOC. 2006,128:10376-10377
[33] Mason B. P., Bogdan A. R., Goswami A., and McQuade D. T. A General Approach to Creating Soluble Catalytic Polymers Heterogenized in Microcapsules [J]. Org. Lett.,2007,9( 17):3449-3451
[34] Deratani, A.; Darling, G. D.; Horak, D.; Frechet, J. M.Heterocyclic Polymers as Catalysts in Organic Synthesis. Effect of Macromolecular Design and Microenvironment on the Catalytic Activity of Polymer-Supported (Dialky1amino)pyridine Catalysts[J]. Macromolecules1987, 20:767-772
[35] Menger, F. M.; McCann, D. J. A Polymer-Bound 4-Aminopyridine: Synthesis and Reactivity [J].J. Org. Chem. 1985, 50:3928-3930
[36]黄积涛孙经武曹爱丽张嘉琪高分子酰化催化剂聚4-3-吡咯啉基吡啶的合成[J].化学世界, 1996, 7:367-370
[37] Mammen M, Dahmann G, and George M, Whitesides Effective Inhibitors of Hemagglutination by Influenza Virus Synthesized from Polymers HavingActive Ester Groups.[J].J. Med. Chem., 1995, 38 (21):4179-4190
[38] Pollak A; Blumenfeld H; Wax M; Baughn R L; Whitesides G M Enzvme Immobilization bv Condensation Copolvmerization into cross-Linked Polyacryiamide Gels. [J].J.Am.Chem.SOC.1980, 102:6324-6336
[39] Weitkamp J, Hunger M, Rymsa U Base catalysis on microporous and mesoporous materials: recent progress and perspectives [J]. Microporous and Mesoporous Materials 2001, 48:255-270
[40] Cauvel A, Renard G, Brunel D Monoglyceride Synthesis by Heterogeneous Catalysis Using MCM-41 Type Silicas Functionalized with Amino Groups [J].J. Org. Chem. 1997, 62:749-751
[41] ZHANG Xue-Hong, CHEN Bing, WEI Wei, SUN Yu-Han Preparation of Functionalized Porous Silica by Ultrasonic Technique for the Methylation Reaction of Phenol with Dimethyl Carbonate [J]. Chinese Journal of Chemistry 2005 23 (10): 1376-1380
[42] Ochiai E Recent Japanese work on the chemistry of pyridine 1-oxide and related compounds [J]. J Org Chem., 1953, 18:534-551。
[43]朱秋华,陈卫民4-硝基吡啶N-氧化物制备方法的改进[J].中国医药工业杂志, 2000,31 (2):556- 557.
[44]任勇,刘静. 4-氨基吡啶的合成[J].化学试剂, 1998 , 20(4):240- 241.
[45]王志祥,张志炳. 4-氨基吡啶合成的改进[J].中国医药工业杂志, 2001, 32 (2):83- 84.
[46]张红艳,刘尚远,赵增国N -氧化-4-硝基吡啶的合成及表征[J].天津师范大学学报(自然科学版),2004,24(4):12-13.
[47]杨春常,范平,黄治清,等.对氨基吡啶的合成与研究[J].辽宁化工, 1991, 28 (3): 36237.
[48] Edward J, Delaney, Wood L E, Irving M Klotz Poly(ethylenimines) with Alternative (Alky1amino)pyridines as Nucleophilic Catalysts [J].J. Am. Chem. SOC. 1982,104:799-807
[49]李乐平段学民陈立功N-烷基-3-吡咯酮类化合物的合成[J].精细化工,2005,22(2):158-160