化工学报 ›› 2013, Vol. 64 ›› Issue (8): 2875-2882.doi: 10.3969/j.issn.0438-1157.2013.08.025

• 催化、动力学与反应器 • 上一篇    下一篇

醛/氨反应合成吡啶碱机理

张弦, 罗才武, 黄登高, 李安, 刘娟娟, 晁自胜   

  1. 湖南大学化学化工学院, 化学生物传感与计量学国家重点实验室, 湖南 长沙 410082
  • 收稿日期:2012-12-28 修回日期:2013-05-03 出版日期:2013-08-05
  • 通讯作者: 晁自胜 E-mail:zschao@huu.edu.cn
  • 作者简介:张弦(1983- ),男,博士研究生。
  • 基金资助:

    湖南省芙蓉学者奖励计划项目;教育部创新团队(湖南大学)项目(IRT1238)。

Reaction mechanism of aldehydes and ammonia to form pyridine bases

ZHANG Xian, LUO Caiwu, HUANG Denggao, LI An, LIU Juanjuan, CHAO Zisheng   

  1. State Key Laboratory of Chemo/Biosensing and Chemometrics, School of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, Hunan, China
  • Received:2012-12-28 Revised:2013-05-03 Online:2013-08-05
  • Supported by:

    supported by the Program for Lotus Scholar in Hunan Province and the Program for Innovative Research Team(Hunan University)of MOE(IRT1238).

摘要: 在常压釜式反应器中,以乙酸为溶剂,开展了乙酸铵(氨源)与甲醛、乙醛和丙烯醛中的一种或多种反应制备吡啶碱的研究。通过Hückel和Mulliken模型的量子化学和热力学计算,分析了丙烯醛和反应中间体丙烯亚胺的构型和电荷,考察了生成中间体二氢吡啶和产物3-甲基吡啶过程中的静电相互作用、前线分子轨道和能量变化,从而提出了丙烯醛/氨合成3-甲基吡啶的反应机理,并总结了醛/氨反应制吡啶碱反应的一般规律。理论预测的产物组成与实验结果具有良好的一致性。

关键词: 醛, 吡啶碱, 烯亚胺, 二氢吡啶

Abstract: Pyridine bases were prepared by reactions of aldehydes(formaldehyde,acrolein and/or acetaldehyde)with ammonium acetate,using acetic acid as solvent,in a refluxing tank reactor under atmospheric pressure.Quantum chemical and thermodynamic calculations were conducted to analyze the configurations and charges of acrolein and propylene imine and to investigate the electrostatic interaction,frontier molecular orbital and energy changes during the formations of intermediate dihydropyridine and product 3-methyl pyridine.Based on these results,a reaction mechanism was proposed for the formation of 3-methyl pyridine from acrolein and ammonia,and also,a general rule was summarized for the reaction of aldehyde with ammonia to form pyridine bases.The products distribution predicted theoretically was consistent with that obtained by experiment.

Key words: aldehyde, pyridine bases, alkenyl imine, dihydropyridine

中图分类号: 

  • O626.32
[1] Kalevaru V N,Madaan N,Martin A.Synthesis,characterization and catalytic performance of titania supported VPO catalysts for the ammoxidation of 3-picoline[J].Applied Catalysis A:General,2011,391(1/2):52-62
[2] Chuck R.Technology development in nicotinate production[J].Applied Catalysis A:General,2005,280:75-82
[3] Wang Qi(王齐),Yang Yi(杨亿),Xiao Guomin(肖国民).Application and technical development of 3-methylpyridine derivates[J].Chemical Technology Market(化工科技市场),2005,2:26-29
[4] Fang J,Yugang C,Zebao R,Yongdan L.Effect of sequential desilication and dealumination on catalytic performance of ZSM-5 catalyst for pyridine and 3-picoline synthesis[J].Journal of Materials Research,2010,25(2):272-282
[5] Huan Z,Guomin X,Jianhua L.Separatic of picolines by dissociation extraction[J].Journal of Southeast University,2005,21(1):68-72
[6] Helmut B,Hans S,Gerd S,Wilhelm A S,Wolfgang W. Catalyst for the production of pyridine and 3-methylpyridine:US,3960766.1976-06-01
[7] Kenneth R H.Production of β-picoline[P]:GB,896049. 1962-05-09
[8] Yoshiaki N,Akio N,Yasukazu M.Process for producing pyridine bases[P]:US,3580917.1971-03-25
[9] Helmut B,Heinz F.Process for the production of 3-methyl pyridine[P]:US,4163854.1979-08-07
[10] Asrian N.Manufacture of pyridine bases[P]:GB,1240928.1971-07-28
[11] Zhang Xian(张弦),Pan Jingang(潘金钢),Chao Zisheng(晁自胜),Li Guoqiang(李国强),Wang Kaiming(王开明).A new method of preparing 3-picoline from acrolein[P]:CN,102249989.2011-11-23
[12] Calvin J R,Davis R D,McAteer C H.Mechanistic investigation of the catalyzed vapor-phase formation of pyridine and quinoline bases using 13CH2O,13CH3OH,and deuterium-labeled aldehydes[J].Applied Catalysis A:General,2005,285:1-23
[13] Baldev S,Sisir K R,Krishnadeo P S,Tarun K G.Role of acidity of pillared inter-layered clay(PILC)for the synthesis of pyridine bases[J].Journal of Chemical Technology and Biotechnology,1998,71(3):246-252
[14] Jiang Jie(蒋劼),Mao Dongsen(毛东森),Yang Weimin(杨为民),Lu Guanzhong(卢冠忠).Catalytic synthesis of alkylpyridine over Co/ZSM-5 zeolite[J].Industrial Catalysis(工业催化),2003,11(8):32-37
[15] Tschitschibabin A E,Oparina M P.The analysis of reaction products,which form during the heating of the aldehyde-to paraldehyds[J].Journal of Research in Physical Chemistry and Chemical Physics,1924,107(5/6/7/8):138-144
[16] Tschitschibabin A E,Oparina M P.The condensation of crotonaldehyde with ammonia in the presence of aluminum oxid[J].Reports of the German Chemical Society,1927,60(8):1877-1879
[17] Tschitschibabin A E,Oparina M P.Condensation of propionaldehyde with ammonia[J].Journal of Research in Physical Chemistry and Chemical Physics,1924,107(5/6/7/8):145-154
[18] Tschitschibabin A E,Oparina M P.Condensation of acetaldehyde and paraldehyds with aniline in the presence of aluminum oxide as a contact substance[J].European Journal of Inorganic Chemistry,1927,60(8):1873-1876
[19] Sisir K R,Banikar G,Shyam K R.Studies on the synthesis of 2 & 4-picoline-correlation of acidity with the catalytic activity[J].Studies in Surface Science and Catalysis,1998, 113:713-719
[20] Farberov M I,Ustavshchikov B F.Synthesis of pyridine bases from aldehydes and ammonia(review)[J].Chemistry of Heterocyclic Compounds,1975,11(12):1349-1353
[21] Farberov M I,Kutin A M,Ustavshchikov B F,Shemyakina N K.Synthesis of pyridine compounds from paraldehyde and ammonia[J].Russian Journal of Applied Chemistry,1964,37(3):661-668
[22] Strain H H.Liphatic ammono aldehydes[J].Journal of the American Chemical Society,1932,54(3):1221-1228
[23] Jie J L. Chichibabin Pyridine Synthesis,Name Reactions in Heterocyclic Chemistry[M].Canada:John Wiley & Sons Inc.,2009:107-109
[24] Anil S,Sanjay K,Jagir S S.Hantzsch reaction:recent advances in Hantzsch 1,4-dihydropyridines[J].Journal of Scientific and Industrial Research,2008,67(2):95-111
[25] James I G,Rolf D.Process for the production of 3-picoline[P]:US,4421921.1983-12-20
[1] 王岩, 石磊, 范家麒, 陈飞, 姚杰, 许光文. 环丁砜处理磺酸树脂高效催化聚甲氧基二甲醚合成[J]. 化工学报, 2019, 70(1): 116-127.
[2] 李海涛, 牛珠珠, 杨国峰, 张鸿喜, 王志鹏, 赵永祥. Cu2O/TiO2催化甲醛乙炔化反应的载体效应[J]. 化工学报, 2018, 69(6): 2512-2518.
[3] 吕喜蕾, 阮厚航, 陈皓, 吕秀阳. 近临界乙醇中Zr-SBA-15催化糠醛一步法制备乙酰丙酸乙酯[J]. 化工学报, 2018, 69(6): 2488-2495.
[4] 周峰, 刘宏臣, 王克军, 温正慧, 陈光文. 连续流微反应器中简单咪唑的制备[J]. 化工学报, 2018, 69(6): 2481-2487.
[5] 梁兴唐, 钟书明, 刘子杰, 郑韵英, 张瑞瑞, 焦淑菲, 廖日权, 王芸, 尹艳镇. 甲壳素/聚乙烯亚胺复合物对水溶液中Cr(Ⅵ)的吸附[J]. 化工学报, 2018, 69(5): 2255-2262.
[6] 夏盛杰, 罗伟, 薛继龙, 孟跃, 蒋军辉, 倪哲明. In/Au(111)和Ir/Au(111)面上巴豆醛选择加氢的机理研究及比较[J]. 化工学报, 2018, 69(4): 1476-1483.
[7] 毛明, 冷尔唯, 龚勋, 徐明厚. [Bmim]Cl中CrCl3-AlCl3催化纤维素降解制取5-羟甲基糠醛[J]. 化工学报, 2018, 69(2): 801-807.
[8] 孙雪飞, 高勇强, 赵颂, 张文, 王志, 王晓琳. 胍基聚合物接枝改性制备抗菌抗污染超滤膜[J]. 化工学报, 2018, 69(11): 4869-4878.
[9] 董金鑫, 朱召贤, 姚鸿俊, 龙东辉. 酚醛气凝胶/碳纤维复合材料的结构调控及性能研究[J]. 化工学报, 2018, 69(11): 4896-4901.
[10] 赵国冰, 张琪, 程飞, 王天宇. Na改性Pt/AlOOH对甲醛催化氧化反应活性的影响[J]. 化工学报, 2018, 69(11): 4722-4727.
[11] 朱晓兵, 金灿, 李小松, 刘景林, 刘晨阳, 刘潇钰. LED可见光下Au/TiO2光催化氧化甲醛表观动力学[J]. 化工学报, 2017, 68(S1): 196-203.
[12] 许波, 陈振乾. 建材内甲醛散发参数处理方法及实验研究[J]. 化工学报, 2017, 68(S1): 43-47.
[13] 李术艳, 孙莉娜, 沈淑君, 程天行, 程双华, 陈久喜. 二芳基二硫醚与硝基芳烃的反应[J]. 化工学报, 2017, 68(6): 2394-2398.
[14] 李颖, 刘肖红, 安华良, 赵新强, 王延吉. Ni/La-Al2O3的制备及催化正丁醛“一锅法”合成辛醇反应性能[J]. 化工学报, 2017, 68(4): 1381-1389.
[15] 武倩倩, 叶春梅, 廖艳梅, 张安伦, 朱英红, 马淳安. 对丙烯基茴香醚的直接电氧化活化[J]. 化工学报, 2017, 68(4): 1660-1666.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
No Suggested Reading articles found!