Citation: CHAI Yongzhen, CHANG Yu, SONG Ruiqin, LIU Wei, LI Yunhui, PAN Lihua. Synthesis and Characterization of Dimethyl 6, 6'-Dimethyl-[2, 2'-bipyridine]-4, 4'-dicarboxylate[J]. Chinese Journal of Applied Chemistry, ;2017, 34(2): 146-150. doi: 10.11944/j.issn.1000-0518.2017.02.160163 shu

Synthesis and Characterization of Dimethyl 6, 6'-Dimethyl-[2, 2'-bipyridine]-4, 4'-dicarboxylate

CHAI Yongzhen ^a ,
CHANG Yu ^b ,
SONG Ruiqin ^a ,
LIU Wei ^a ,
LI Yunhui ^a,*,, ,
PAN Lihua ^b,*,,

a.
College of Chemical and Environmental Engineering, Changchun University of Science and Technology, Changchun 130022, China
b.
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China

Corresponding author: LI Yunhui, liyh@cust.edu.cn PAN Lihua, lihuap@ciac.ac.cn
Received Date: 15 April 2016
Revised Date: 17 June 2016
Accepted Date: 5 July 2016

Fund Project: the Project of Jilin Provincial Development and Reform Commission 2014Y115the Key Science and Technology Project of Jilin Province 20150204010YY

Figures(4)

Dimethyl 6, 6'-dimethyl-[2, 2'-bipyridine]-4, 4'-dicarboxylate was synthesized in two steps from methyl 6-methyl-2-hydroxypyridine-4-carboxylate. The first step was the preparation of methyl 2-methyl-6-[(p-toluenesulfonyl) oxy]pyridine-4-carboxylate by esterification. The second step was to prepare the target product by nickel complex catalyzed homocoupling reaction. Several other factors which affected the reaction such as material proportion, reaction temperature and addition order were investigated. When the reaction was carried out under the optimal conditions, 77% yield was achieved. The products were characterized by nuclear magnetic resonance (NMR), Fourier transform infrared spectrometer (FTIR), mass spectrometry (MS) and differential scanning calorimetry (DSC) to prove the reliability of the synthetic method. This structure can fully satisfy the need of chelating agent intermediate for homogeneous time-resolved fluoroimmunoassay (HTRF), which has been succeeded in prectical applications.
- homogeneous time-resolved fluoroimmunoassay,
- homocoupling,
- dimethyl dimethyl-[bipyridine]-dicarboxylate
1. [1]
  Cordaro J G, McCusker J K, Bergman R G. Synthesis of Mono-substituted 2, 2'-Bipyridines[J]. Chem Commun, 2002,14:1496-1497.
2. [2]
  Bass P, Purdon R A, Patterson M A. Gastric Antisecretory and Other Pharmacologic Studies on 2, 2'-Bipyridine[J]. J Pharmacol Exp Ther, 1966,152(152):104-115.
3. [3]
  Kaes C, Katz A, Hosseini M W. Bipyridine:The Most Widely Used Ligand. A Review of Molecules Comprising at Least Two 2, 2'-Bipyridine Units[J]. Chem Rev, 2000,100(10):3553-3590. doi: 10.1021/cr990376z
4. [4]
  LI Haiyan, LI Yunhui, PAN Lihua. Preparation and Characterization of a Novel Type Complex[J]. Chinese J Appl Chem, 2010,27(9):1008-1011.
5. [5]
  Alpha B, Anklam E, Deschenaux R. Synthesis and Characterisation of the Sodium and Lithium Cryptates of Macrobicyclic Ligands Incorporating Pyridine, Bipyridine, and Biisoquinoline Units[J]. Helv Chim Acta, 1988,71:1042-1052. doi: 10.1002/(ISSN)1522-2675
6. [6]
  Penalva V, Hassan J, Lavenot L. Direct Homocoupling of Aryl Halides Catalyzed by Palladium[J]. Tetrahedron Lett, 1998,39:2559-2560. doi: 10.1016/S0040-4039(98)00196-8
7. [7]
  Tiecco M, Testaferri L, Tingoli M. A Convenient Synthesis of Bipyridines by Nickel-phosphine Complex-Mediated Homo Coupling of Halopyridines[J]. Synthesis, 1984,16(9):736-738.
8. [8]
  Vanderesse R, Lourak M, Fort Y. Activation of Reducing Agents. Sodium Hydride Containing Complex Reducing Agents 23.Symmetrical Coupling of Nitrogen-containing Heterocyclic Halides[J]. Tetrahedron Lett, 1986,27(45):5483-5486. doi: 10.1016/S0040-4039(00)85243-0
9. [9]
  Fort Y, Becker S, Caubere P. A Convenient Synthetic Route to Bis-heteroaromatic and Bis-heterocyclic Compounds Promoted by Liganded Nickel Complex Reducing Agents[J]. Tetrahedron, 1994,50(41):11893-11902. doi: 10.1016/S0040-4020(01)89303-0
10. [10]
  HONG Ran. Nickel Catalyst Ullmann Coupling Reaction of the Preliminary Study and Crystal Morphology Effect of the Hydrogen Acceptor in the Catalytic Transfer Hydrogenation[D]. Shanghai:Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 2001(in Chinese).
11. [11]
  QIAN Yanlong, WANG Chen, TAO Xiaochun. Synthesis of 2, 2'-Bipyridine Through Catalitic Coupling Reaction of α-Brompyridine Using Nickel Complex[J]. J Org Chem, 2003,23(11):1264-1266.
12. [12]
  Cornella J, Gómez-Bengoa E, Martin R. Combined Experimental and Theoretical Study on the Reductive Cleavage of Inert C-O Bonds with Silanes:Ruling out a Classical Ni (0)/Ni (Ⅱ) Catalytic Couple and Evidence for Ni (Ⅰ) Intermediates[J]. J Am Chem Soc, 2013,135(5):1997-2009. doi: 10.1021/ja311940s
13. [13]
  Lanni E L, McNeil A J. Mechanistic Studies on Ni (dppe) Cl₂-catalyzed Chain-growth Polymerizations:Evidence for Rate-determining Reductive Elimination[J]. J Am Chem Soc, 2009,131(45):16573-16579. doi: 10.1021/ja904197q
14. [14]
  Amatore C, Jutand A. Rates and Mechanism of Biphenyl Synthesis Catalyzed by Electrogenerated Coordinatively Unsaturated Nickel Complexes[J]. Organometallics, 1988,7(10):2203-2214. doi: 10.1021/om00100a019
15. [15]
  LI Zhe. Mechanisms of Palladium and Nickel Catalyzed Cross Coupling Reactions[D]. Hefei:University of Science and Technology of China, 2009(in Chinese).
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