Citation: HUI Wenping, LIU De'e, HOU Dan, CHEN Zhanguo. Synthesis of 2-Oxazoline Derivatives from Ethyl α-Cyanocinnamate Derivatives and N-Bromobenzamide[J]. Chinese Journal of Applied Chemistry, ;2017, 34(7): 757-767. doi: 10.11944/j.issn.1000-0518.2017.07.160419 shu

Synthesis of 2-Oxazoline Derivatives from Ethyl α-Cyanocinnamate Derivatives and N-Bromobenzamide

Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China

Corresponding author: CHEN Zhanguo, chzhg@snnu.edu.cn
Received Date: 18 October 2016
Revised Date: 23 December 2016
Accepted Date: 21 February 2017

Fund Project: the National Natural Science Foundation of China 20572066the Natural Science Foundation of Shaanxi Province 2009JM2001the Innovation Foundation of Postgraduate Cultivation of Shaanxi Normal University 2008CXB009

Figures(8)

2-Oxazoline derivative belongs to an important class of heterocyclic compounds, new synthetic method and new 2-oxazoline derivatives are eagerly desired. In order to develop a new protocol for the synthesis of deferent structural 2-oxazoline derivatives, a method from ethyl α-cyanocinnamate derivatives and N-bromobenzamide has been explored. The structures of all eleven synthesized products were confirmed by proton nuclear magnetic resonance spectroscopy(¹H NMR), and mass spectrometry(MS). The results show that a series of ethyl α-cyanocinnamate derivatives(3a~3k) can be smoothly converted into corresponding 2-oxazoline derivatives(5a~5k). When Na₂CO₃ was used as the promoter in acetone at room temperature, the corresponding products were obtained in high yield(up to 90%). Not only can ethyl α-cyanocinnamate derivatives be used as substrate, but also ethyl α-carbethoxy-cyanocinnamate(6) can be employed as the substrate, too. Experiment results indicate that N-bromo-p-nitrobenzamide(8) and N-bromoacetamide(9) can tolerate this reaction except N-bromobenzamide(4). Above results indicate that the easy and efficient protocol has application in a large scope of electron-deficient olefins and N-bromoamide. A possible mechanism was proposed which can explain well the full regiospecificity of the reaction.
- ethyl α-cyanocinnamate,
- N-bromobenzamide,
- oxazoline derivative
1. [1]
  Braga A L, Galetto F Z, Taube P S. Mild and Efficient One-Pot Synthesis of Chiral β-Chalcogen Amides via 2-Oxazoline Ring-Opening Reaction Mediated by Indium Metal[J]. J Organomet Chem, 2008,693(24):3563-3566. doi: 10.1016/j.jorganchem.2008.08.031
2. [2]
  Reddy L R, Saravanan P, Corey E J. A Simple Stereocontrolled Synthesis of Salinosporamide A[J]. J Am Chem Soc, 2004,126j(20):6230-6231.
3. [3]
  Saravanan P, Corey E J. A Short, Stereocontrolled, and Practical Synthesis of Alpha-Methylomuralide, a Potent Inhibitor of Proteasome Function[J]. J Org Chem, 2003,68(7):2760-2764. doi: 10.1021/jo0268916
4. [4]
  Kobayashi S, Fujikawa S I, Ohmae M. Enzymatic Synthesis of Chondroitin and Its Derivatives Catalyzed by Hyaluronidase[J]. J Am Chem Soc, 2003,125(47):14357-14369. doi: 10.1021/ja036584x
5. [5]
  Hargaden G C, Guiry P. Recent Applications of Oxazoline-containing Ligands in Asymmetric Catalysis[J]. Chem Rev, 2009,109(6):2505-2550. doi: 10.1021/cr800400z
6. [6]
  Desimoni G, Faita G, Jrgensen K A. C₂-Symmetric Chiral Bis(oxazoline) Ligands in Asymmetric Catalysis[J]. Chem Rev, 2006,106(9):3561-3651. doi: 10.1021/cr0505324
7. [7]
  Frump J A. Oxazolines. Their Preparation, Reactions, and Applications[J]. Chem Rev, 1971,71(5):483-506. doi: 10.1021/cr60273a003
8. [8]
  Kangani C O, Day B W. A Novel and Direct Synthesis of 1, 3, 4-Oxadiazoles or Oxazolines from Carboxylic Acids Using Cyanuric Chloride/Indium[J]. Tetrahedron Lett, 2009,50(38):5332-5335. doi: 10.1016/j.tetlet.2009.07.032
9. [9]
  Zhou P W, Blubaum J E, Bums C T. The Direct Synthesis of 2-Oxazolines from Carboxylic Esters Using Lanthanide Chloride as Catalyst[J]. Tetrahedron Lett, 1997,38(40):7019-7020. doi: 10.1016/S0040-4039(97)01641-9
10. [10]
  Ohshima T, Iwasaki T, Mashima K. Direct Conversion of Esters, Lactones, and Carboxylic Acids to Oxazolines Catalyzed by a Tetranuclear Zinc Cluster[J]. Chem Commun, 2006(25):2711-2713. doi: 10.1039/b605066b
11. [11]
  Mei L, Hai Z J, Jie S. Modular Synthesis of Oxazolines and Their Derivatives[J]. J Comb Chem, 2009,11(2):220-227. doi: 10.1021/cc8001537
12. [12]
  Baltork I M, Moghadam M, Tangestaninejad S. Environmental-Friendly Synthesis of Oxazolines, Imidazolines and Thiazolines Catalyzed by Tungstophosphoric Acid[J]. Catal Commun, 2008,9(6):1153-1161. doi: 10.1016/j.catcom.2007.10.026
13. [13]
  Chaudhry P, Schoenen F, Neuenswander B. One-Step Synthesis of Oxazoline and Dihydrooxazine Libraries[J]. J Comb Chem, 2007,9(3):473-476. doi: 10.1021/cc060159t
14. [14]
  Schwekendiek K, Glorius F. Efficient Oxidative Synthesis of 2-Oxazolines[J]. Synthesis, 2006(18):2996-3002.
15. [15]
  Wuts P G M, Northuis J M, Kwan T A. The Synthesis of Oxazolines Using the Vilsmeier Reagent[J]. J Org Chem, 2000,65(26):9223-9225. doi: 10.1021/jo000664r
16. [16]
  Hajra S, Bar S, Sinha D. Stereoselective One-Pot Synthesis of Oxazolines[J]. J Org Chem, 2008,73(11)432014322.
17. [17]
  Minakata S, Morino Y, Ide T. Direct Synthesis of Oxazolines from Olefins and Amides Using t-BuOI[J]. Chem Commun, 2007(31):3279-3281. doi: 10.1039/b706572h
18. [18]
  Chen Z G, Wang Y, Wei J F. K₃PO₄-catalyzed Regiospecific Aminobrominationof β-Nitrostyrene Derivatives with N-Bromoacetamide as Aminobrominating Agent[J]. J Org Chem, 2010,75(6):2085-2088. doi: 10.1021/jo9026879
19. [19]
  Chen Z G, Zhao P F, Wang Y. Aminobromination of β-Nitrostyrene Derivatives with N, N-Dibromourethane as the Aminobrominating Reagent[J]. Eur J Org Chem, 2011:5887-5893.
20. [20]
  CHEN Zhanguo, WANG Yingjie, LIU De'e. α, β-Vicinal Bromoamine Compounds Converted into α, β-Dehydroamino Derivatives Promoted by Combination of Potassium Carbonate and Thiouea in Water[J]. Chem J Chinese Univ, 2014,35(7):1458-1464. doi: 10.7503/cjcu20131129
21. [21]
  Chen Z G, Liu Y L, Hu J L. Aminobromination of Ethyl α-Cyanocinnamate Derivatives with 1, 3-Dibromo-5, 5-dimethylhydantoin(DBDMH) as Nitrogen and Halogen Sources[J]. Chem Res Chinese Univ, 2015,31(1):65-70. doi: 10.1007/s40242-015-4341-x
22. [22]
  LIU Yali, LIU De'e, DU Manfei. High Regioselective Aminobromination of β-Nitrostyrene Derivatives with 1, 3-Dibromo-5, 5-dimethyl Hydantoin[J]. Chem J Chinese Univ, 2015,36(6):1117-1125.
23. [23]
  Chen Z G, Du M F, Xia W. One-Pot Synthesis of α, β-Dehydroamino Derivatives from β, β-Dicyanostyrene with 1, 3-Dibromo-5, 5-Dimethylhydantoin Promoted by Mild Base[J]. Chem Res Chinese Univ, 2016,32(1):68-75. doi: 10.1007/s40242-016-5233-4
24. [24]
  Sun Q, Shi L X, Ge Z M. An Efficient and Green Procedure for the Knoevenagel Condensation Catalyzed by Urea[J]. Chinese J Chem, 2005,23(6):745-748. doi: 10.1002/(ISSN)1614-7065
25. [25]
  Rao P S, Venkataratnam R V. Zinc Chloride as a New Catalyst for Knoevenagel Condensation[J]. Tetrahedron Lett, 1991,32(41):5821-5822. doi: 10.1016/S0040-4039(00)93564-0
26. [26]
  Gomes M N, De O C M A, Garrote C F D. Condensation of Ethyl Cyanoacetate with Aromatic Aldehydes in Water, Catalyzed by Morpholine[J]. Synth Commun, 2011,41(1):52-57.
27. [27]
  Yue C B, Mao A Q, Wei Y Y. Knoevenagel Condensation Reaction Catalyzed by Task-Specific Ionic Liquid under Solvent-free Conditions[J]. Catal Commun, 2008,9(7):1571-1574. doi: 10.1016/j.catcom.2008.01.002
28. [28]
  Li G W, Xiao J, Zhang W Q. Knoevenagel Condensation Catalyzed by a Tertiary-Amine Functionalized Polyacrylonitrile Fiber[J]. Green Chem, 2011,13(7):1828-1836. doi: 10.1039/c0gc00877j
29. [29]
  Rong L G, Li X Y, Wang H Y. Efficient Green Procedure for the Knoevenagel Condensation under Solvent-Free Conditions[J]. Synth Commun, 2006,36(16):2407-2412. doi: 10.1080/00397910600640289
30. [30]
  Cao Y Q, Dai Z, Zhang R. A Practical Knoevenagel Condensation Catalyzed by PEG-400 and Anhydrous K₂CO₃ without Solvent[J]. Synth Commun, 2004,34(16):2965-2971. doi: 10.1081/SCC-200026650
31. [31]
  Sandhar R K, Sharma J R, Manrao M R. Reaction of Active Methylene Compounds with 4-Fluorobenzalanilines and Antifungal Potential of the Products[J]. J Indian Chem Soc, 2006,83(3):263-265.
32. [32]
  Zabicky J. The Kinetics and Mechanism of Carbonyl-Methylene Condensation Reactions XI.Stereochemistry of the Products[J]. J Chem Soc, 1961:683-687.
33. [33]
  Hopkins C Y, Chisholm M, Michael R. α-Cyano-β-Arylacrylic Acids[J]. Can J Res, Sect B:Chem Sci, 1945,23B:84-87.
34. [34]
  Kajigaeshi S, Nakagawa T, Fujiaki S. Synthesis of Novel Nickel-Hectorite Inorganic Complexes[J]. Chem Lett, 1988,17(12):2045-2046. doi: 10.1246/cl.1988.2045
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