N-NH2作为导向基的碳氢键官能化任务书

 2022-02-02 09:02

全文总字数:6152字

1. 毕业设计(论文)的内容和要求

三嗪类化合物是一类含氮杂环化合物,在化工染料、材料方面应用广泛,且是杀虫剂、除草剂中重要的组成结构。

近十年来发现其在抗炎、抗高血压、抑制血小板的生成及抑菌方 面也有着显著作用,因此是一类重要的医药中间体。

本课题即以1-甲基-1-苯肼和恶二唑酮在三价铑的催化作用下生成1,2,4-三嗪为模板反应探索该反应的普适性。

剩余内容已隐藏,您需要先支付后才能查看该篇文章全部内容!

2. 实验内容和要求

1.条件优化通过对不同条件的筛选(诸如改变酸,添加剂等)从而得出1,2,4-三嗪产率最高的条件2.底物拓展通过在1-甲基-1-苯肼或恶二唑酮加入不同的取代基(给电子或吸电子或大位阻)来研究该反应的普适性3.机理探索通过动力学同位素试验等来探索反应的机理

3. 参考文献

1. Congreve, M.; Andrews, S. P.; Dore, A. S.; Hollenstein, K.; Hurrell, E.; Langmead, C. J.; Mason, J. S.; Ng, I. W.; Tehan, B.; Zhukov, A.; Weir, M.; Marshall, F. H., Discovery of 1,2,4-triazine derivatives as adenosine A(2A) antagonists using structure based drug design. J Med Chem 2012, 55, 1898-903.2. Dowling, M. S.; Jiao, W.; Hou, J.; Jiang, Y.; Gong, S., Modular Synthesis of 3,6-Disubstituted-1,2,4-triazines via the Cyclodehydration of beta-Keto- N-acylsulfonamides with Hydrazine Salts. J Org Chem 2018, 83, 4229-4238.3. Kamber, D. N.; Liang, Y.; Blizzard, R. J.; Liu, F.; Mehl, R. A.; Houk, K. N.; Prescher, J. A., 1,2,4-Triazines Are Versatile Bioorthogonal Reagents. J Am Chem Soc 2015, 137, 8388-91.4. Meng, J.; Wen, M.; Zhang, S.; Pan, P.; Yu, X.; Deng, W. P., Unexpected O-H Insertion of Rhodium-Azavinylcarbenes with N-Acylhydrazones: Divergent Synthesis of 3,6-Disubstituted- and 3,5,6-Trisubstituted-1,2,4-Triazines. J Org Chem 2017, 82, 1676-1687.5. Crespin, L.; Biancalana, L.; Morack, T.; Blakemore, D. C.; Ley, S. V., One-Pot Acid-Catalyzed Ring-Opening/Cyclization/Oxidation of Aziridines with N-Tosylhydrazones: Access to 1,2,4-Triazines. Org Lett 2017, 19, 1084-1087.6. Baolu Shi, W. L., Ian B. Campbell, and Christopher J. Moody, A Concise Route to Pyridines fromHydrazides by Metal Carbene N-HInsertion, 1,2,4-Triazine Formation, andDiels-Alder Reaction. Org Lett 2009, 11, 3686-3688.7. Li, H.; Zhang, S.; Feng, X.; Yu, X.; Yamamoto, Y.; Bao, M., Rhodium(III)-Catalyzed Oxidative [3 2] Annulation of 2-Acetyl-1-arylhydrazines with Maleimides: Synthesis of Pyrrolo[3,4-b]indole-1,3-diones. Org Lett 2019, 21, 8563-8567.8. Liu, B.; Fan, Y.; Gao, Y.; Sun, C.; Xu, C.; Zhu, J., Rhodium(III)-catalyzed N-nitroso-directed C-H olefination of arenes. High-yield, versatile coupling under mild conditions. J Am Chem Soc 2013, 135, 468-73.9. Liu, B.; Song, C.; Sun, C.; Zhou, S.; Zhu, J., Rhodium(III)-catalyzed indole synthesis using N-N bond as an internal oxidant. J Am Chem Soc 2013, 135, 16625-31.10. Lorion, M.; Guillaumet, G.; Briere, J. F.; Suzenet, F., Sequential Michael Addition and Enamine-Promoted Inverse Electron Demanding Diels-Alder Reaction upon 3-Vinyl-1,2,4-triazine Platforms. Org Lett 2015, 17, 3154-7.11. Lukin, A.; Vedekhina, T.; Tovpeko, D.; Zhurilo, N.; Krasavin, M., Zn-catalyzed hydrohydrazination of propargylamides with BocNHNH2: a novel entry into the 1,2,4-triazine core. RSC Advances 2016, 6, 57956-57959.12. Lv, N.; Chen, Z.; Liu, Z.; Zhang, Y., Redox-Neutral Rhodium(III)-Catalyzed Annulation of Arylhydrazines with Sulfoxonium Ylides To Synthesize 2-Arylindoles. J Org Chem 2019, 84, 13013-13021.13. Pander, P.; Bulmer, R.; Martinscroft, R.; Thompson, S.; Lewis, F. W.; Penfold, T. J.; Dias, F. B.; Kozhevnikov, V. N., 1,2,4-Triazines in the Synthesis of Bipyridine Bisphenolate ONNO Ligands and Their Highly Luminescent Tetradentate Pt(II) Complexes for Solution-Processable OLEDs. Inorg Chem 2018, 57, 3825-3832.14. Song, C.; Yang, C.; Zhang, F.; Wang, J.; Zhu, J., Access to the Cinnoline Scaffold via Rhodium-Catalyzed Intermolecular Cyclization under Mild Conditions. Org Lett 2016, 18, 4510-3.15. Zhou, S.; Wang, J.; Wang, L.; Chen, K.; Song, C.; Zhu, J., Co(III)-Catalyzed, Internal and Terminal Alkyne-Compatible Synthesis of Indoles. Org Lett 2016, 18, 3806-9.16. Zhou, S.; Wang, J.; Zhang, F.; Song, C.; Zhu, J., A Versatile, Traceless C-H Activation-Based Approach for the Synthesis of Heterocycles. Org Lett 2016, 18, 2427-30.17. Chen, Z.; Ren, N.; Ma, X.; Nie, J.; Zhang, F.-G.; Ma, J.-A., Silver-Catalyzed [3 3] Dipolar Cycloaddition of Trifluorodiazoethane and Glycine Imines: Access to Highly Functionalized Trifluoromethyl-Substituted Triazines and Pyridines. ACS Catalysis 2019, 9, 4600-4608.18. Wang, C. Q.; Ye, L.; Feng, C.; Loh, T. P., C-F Bond Cleavage Enabled Redox-Neutral [4 1] Annulation via C-H Bond Activation. J Am Chem Soc 2017, 139, 1762-1765.19. Wu, X.; Wang, B.; Zhou, S.; Zhou, Y.; Liu, H., Ruthenium-Catalyzed Redox-Neutral [4 1] Annulation of Benzamides and Propargyl Alcohols via CH Bond Activation. ACS Catalysis 2017, 7, 2494-2499.20. Wu, X.; Wang, B.; Zhou, Y.; Liu, H., Propargyl Alcohols as One-Carbon Synthons: Redox-Neutral Rhodium(III)-Catalyzed C-H Bond Activation for the Synthesis of Isoindolinones Bearing a Quaternary Carbon. Org Lett 2017, 19, 1294-1297.21. Xing, Y. Y.; Liu, J. B.; Sheng, X. H.; Sun, C. Z.; Huang, F.; Chen, D. Z., Solvent Mediating a Switch in the Mechanism for Rhodium(III)-Catalyzed Carboamination/Cyclopropanation Reactions between N-Enoxyphthalimides and Alkenes. Inorg Chem 2017, 56, 5392-5401.22. Yang, W.; Dong, J.; Wang, J.; Xu, X., Rh(III)-Catalyzed Diastereoselective Annulation of Amides with Quinone Monoacetals: Access to Bridged Nine-Membered Heterocycles via C-H Activation. Org Lett 2017, 19, 616-619.23. Li, S. G.; Han, Z. S.; Viereck, P.; Lee, H.; Kurouski, D.; Senanayake, C. H.; Tsantrizos, Y. S., Metal-Free Cycloetherification by in Situ Generated P-Stereogenic alpha-Diazanium Intermediates: A Convergent Synthesis of Enantiomerically Pure Dihydrobenzooxaphospholes. Org Lett 2017, 19, 894-897.24. Chen, A. Y.; Lu, Q.; Fu, Y.; Sarpong, R.; Stoltz, B. M.; Zhang, H., Isocanthine Synthesis via Rh(III)-Catalyzed Intramolecular CH Functionalization. The Journal of Organic Chemistry 2017, 83, 330-337.25. Chen, W. H.; Gao, X. J.; Gao, X., Methanol-Assisted Phthalimide Ring Opening: Concerted or Stepwise Mechanism? J Phys Chem A 2018, 122, 3115-3119.

4. 毕业设计(论文)计划

见附件

剩余内容已隐藏,您需要先支付 10元 才能查看该篇文章全部内容!立即支付

以上是毕业论文任务书,课题毕业论文、开题报告、外文翻译、程序设计、图纸设计等资料可联系客服协助查找。