ARTICLES

Green Synthesis of 1,5-Benzodiazepines with Multifunctional Groups

  • Mingliang Wang ,
  • Liuyan Yin ,
  • Tiantian Wen ,
  • Xiao Zhang ,
  • Jie Gao ,
  • Lanzhi Wang
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  • College of Chemistry & Materials Science, Hebei Normal University, Key Laboratory of Organic Functional Molecules of Hebei Province, Shijiazhuang 050024
* Corresponding author. E-mail:

Received date: 2021-06-17

  Revised date: 2021-09-03

  Online published: 2021-09-27

Supported by

National Natural Science Foundation of China(21776060)

Abstract

1,5-Benzodiazepine compounds are seven-membered nitrogen heterocyclic compounds with important biological and pharmacological activities. Ester group, carboxyl group, acyl group and aryl group are active groups of 1,5-benzodiazepine compounds. One-pot green synthesis of 34 kinds of 1,5-benzodiazepines with COR, COOR or COOH by three-component tandem reaction was performed at room temperature (25 ℃) with a yield of up to 90%. The mechanism of catalytic tandem reaction was proposed. These reactions were achieved by using aldehyde carbonyl compounds or dicarbonyl compounds, 3-butyn-2-one, substituted o-phenylenediamine as raw materials, absolute ethanol as solvent, magnetic nano cobalt ferrite (CoFe2O4) was realized under catalyst or without catalyst. The multifunctional 1,5-benzodiazepine compounds were formed via Michael addition reaction, nucleophilic addition-dehydration reaction, intramolecular imine-enamine cyclization and proton transfer processes, which realized that multiple active groups such as active acyl, ester or carboxyl groups were simultaneously introduced into the seven-membered ring of the benzodiazepine in a reaction system under mild conditions. This synthesis method has the advantages of novel synthesis method, atom economy, high yield and selectivity of the target compounds, which realize the green reaction process, and provide a new idea for green synthesis of benzozazepines.

Cite this article

Mingliang Wang , Liuyan Yin , Tiantian Wen , Xiao Zhang , Jie Gao , Lanzhi Wang . Green Synthesis of 1,5-Benzodiazepines with Multifunctional Groups[J]. Chinese Journal of Organic Chemistry, 2022 , 42(1) : 160 -171 . DOI: 10.6023/cjoc202106028

References

[1]
Velasco-Rubio, A.; Varela, J. A.; Saa, C. Adv. Synth. Catal. 2020, 362, 4861.
[2]
An, Y. S.; Li, X. Q.; An, X. R.; Wang, L. Z. Monatsh. Chem. 2015, 146, 165.
[3]
Zhang, X. J.; Wang, L. Z.; Yan, J. Y.; Gao, C. Chin. J. Org. Chem. 2017, 37, 462. (in Chinese)
[3]
(张秀君, 王兰芝, 闫婧怡, 高晨, 有机化学, 2017, 37, 462.)
[4]
Arora, N.; Dhiman, P.; Kumar, S.; Singh, G.; Monga, V. Bioorg. Chem. 2020, 97, 35.
[5]
Wang, K. X.; Wang, L. Z. Chin. J. Org. Chem. 2019, 39, 1147. (in Chinese)
[5]
(王凯璇, 王兰芝, 有机化学, 2019, 39, 1147.)
[6]
Indalkar, K. S.; Patil, M. S.; Chaturbhuj, G. U. Tetrahedron Lett. 2017, 58, 4496.
[7]
Nagaraju, B.; Kovvuri, J.; Babu, K. S.; Adiyala, P. R.; Nayak, V. L.; Alarifi, A.; Kamal, A. Tetrahedron 2017, 73, 6969.
[8]
Nejadshafiee, V.; Naeimi, H. Curr. Org. Synth. 2019, 16, 136.
[9]
Anil, S. M.; Shobith, R.; Kiran, K. R.; Swaroop, T. R.; Mallesha, N.; Sadashiva, M. P. New J. Chem. 2019, 43, 182.
[10]
Zhang, K. Y.; Li, J.; Wang, K. X.; An, X. Y.; Wang, L. Z. ChemistrySelect 2020, 5, 14056.
[11]
Hazai, V.; Szabo, T.; Volk, B.; Milen, M. Chem. Heterocycl. Compd. 2020, 56, 237.
[12]
Christophe, C.; Langlois, B. R.; Billard, T. J. Fluorine Chem. 2013, 155, 118.
[13]
Climent, M. J.; Corma, A.; Iborra, S.; Santos, L. L. Chem.-Eur. J. 2009, 15, 8834.
[14]
Du, Y. Y.; Tian, F. L.; Zhao, W. Z. Synth. Commun. 2006, 36, 1661.
[15]
Sharma, S.; Gogoi, P.; Konwar, D. Green Chem. 2007, 9, 153.
[16]
Taghizadeh, M. J.; Malakpouri, G. R.; Javidan, A. J. Iran. Chem. Soc. 2019, 16, 785.
[17]
Sun, Y. W. M.S. Thesis, Hebei Normal University, Shijiazhuang, 2019. (in Chinese)
[17]
(孙悦玮, 硕士论文,河北师范大学, 石家庄, 2019.)
[18]
An, Y. S.; Hao, Z. F.; Zhang, X. J.; Wang, L. Z. Chem. Biol. Drug Des. 2016, 88, 110.
[19]
Bei, Y, M. M.S. Thesis, Hebei Normal University, Shijiazhuang, 2018. (in Chinese)
[19]
(贝月明, 硕士论文, 河北师范大学,石家庄, 2018.)
[20]
Sun, Y. W.; Zhou, L. Y.; Wang, L. Z. Chin. J. Org. Chem. 2019, 39, 3516. (in Chinese)
[20]
(孙悦玮, 周来运, 王兰芝, 有机化学, 2019, 39, 3516.)
[21]
Zhang, M.; Lu, J.; Zhang, J. N.; Zhang, Z. H. Catal. Commun. 2016, 78, 26.
[22]
Chen, M. N.; Mo, L. P.; Cui, Z. S.; Zhang, Z. H. Curr. Opin. Green Sustain. Chem. 2019, 15, 27.
[23]
Lu, J.; Li, X. T.; Ma, E. Q.; Mo, L. P.; Zhang, Z. H. ChemCatChem 2014, 6, 2854.
[24]
Li, X. T.; Zhao, A. D.; Mo, L. P.; Zhang, Z. H. RSC Adv. 2014, 4, 51580.
[25]
Li, J.; Hao, Z. F.; Zhang, K. Y.; Wang, L. Z. Chin. J. Org. Chem. 2021, 41, 806. (in Chinese)
[25]
(李静, 郝振芳, 张凯悦, 王兰芝, 有机化学, 2021, 41, 806.)
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