水介质中活性二氧化锰促进2-氨基苄醇与β-二羰基化合物反应合成喹啉衍生物

doi:10.6023/cjoc202309009

摘要/Abstract

喹啉及其衍生物在农业、医药等领域被广泛应用, 有关它的高效合成方法备受研究者的关注. 报道了一种在水中2-氨基苄醇和β-二羰基化合物合成喹啉衍生物的简单方法, 在活性二氧化锰和空气存在下该反应很容易进行. 底物范围广, 官能团兼容性好. 此外, 水介质中2-氨基苄醇与苯乙酮反应也可以合成相应的喹啉产物, 但需要氢氧化胆碱和活性二氧化锰作为添加剂, 并在50 ℃加热. 这种方法避免使用昂贵且不稳定的醛, 同时以水作为溶剂, 反应过程变得更绿色、经济.

关键词: 喹啉衍生物, 2-氨基苄醇, 活性二氧化锰, 酮, 水

Quinolines derivatives and their syntheses are of great interest owing to their broad applicability in areas from agriculture to medicine. This paper reports a simple method for the synthesis of quinolines from 2-aminobenzyl alcohols and β-dicarbonyl compounds in water. The reaction was easily performed in the presence of active manganese dioxide in air. A broad substrate scope with good functional group tolerance was observed. Furthermore, the corresponding quinoline products can also be obtained from 2-aminophenyl alcohols and acetophenone in water, choline hydroxide and active manganese dioxide as additives and heating at 50 ℃ are required. The method avoids the use of expensive and unstable aldehydes, and uses water as the solvent, making the process more economical and efficient.

Key words: quinolinone derivative, 2-aminobenzyl alcohol, active manganese dioxide, ketone, water

引用此文

王义洪, 李文丽, 林海禄, 乐长高, 谢宗波. 水介质中活性二氧化锰促进2-氨基苄醇与β-二羰基化合物反应合成喹啉衍生物[J]. 有机化学, 2024, 44(5): 1649-1657.

Yihong Wang, Wenli Li, Hailu Lin, Zhanggao Le, Zongbo Xie. Reaction of 2-Aminobenzyl Alcohols with β-Dicarbonyl Compounds to Synthesize Quinoline Derivatives in Water Promoted by Active Manganese Dioxide[J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1649-1657.

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图/表 9

Scheme 1. Structures of some fused quinolines present in natural products and drugs

Scheme 2. Routes used to synthesize quinolines

Entry	MnO₂	Solvent	n(1a)∶n(2a)	Time/h	Yield^b/%
1	3.0	H₂O	1.5∶1.0	24	67
2	3.0	1,4-Dioxane	1.5∶1.0	24	Trace
3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26	3.0 3.0 3.0 3.0 — 0.5 1.0 1.5 2.0 2.5 3.5 4.0 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5	EtOH CH₃CN CH₂Cl₂ DMSO H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O H₂O	1.5∶1.0 1.5∶1.0 1.5∶1.0 1.5∶1.0 1.5∶1.0 1.5∶1.0 1.5∶1.0 1.5∶1.0 1.5∶1.0 1.5∶1.0 1.5∶1.0 1.5∶1.0 1.0∶2.0 1.0∶1.5 1.0∶1.0 1.5∶1.0 2.0∶1.0 3.0∶1.0 2.0∶1.0 2.0∶1.0 2.0∶1.0 2.0∶1.0 2.0∶1.0 2.0∶1.0	24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 10 12 14 16 18 20	18 Trace Trace None Trace 16 27 47 50 64 75 78 54 64 65 72 80 83 56 64 70 74 77 78

Table 1. Optimization of the reaction conditionsa

Scheme 3. Substrate scope of 2-aminobenzyl alcohol and dicarbonyl compounds Reaction conditions: 1a (0.4 mmol), 2a (0.2 mmol), H2O (2 mL), MnO2 (3.5 equiv.), r.t., 18 h. Yield of isolated products.

Scheme 4. Substrate scope of 2-aminobenzyl alcohol and cyclic 1,3-dicarbonyl compounds Reaction conditions: 1a (0.4 mmol), 2a (0.2 mmol), H2O (2 mL), MnO2 (3.5 equiv.), r.t., 18 h. Yield of isolated products.

Scheme 5. Substrate scope of 2-aminobenzyl alcohol and ketone compounds Reaction conditions: 1a (0.4 mmol), 2a (0.2 mmol), H2O (2 mL), MnO2 (3.5 equiv.), ChOH (choline hydroxide, 2.0 equiv.), 50 ℃, 18 h. Yield of isolated products.

Scheme 6. Gram-scale experiment

Scheme 7. Control experiments for exploring the reaction mechanism

Scheme 8. Plausible mechanism for the model reaction

参考文献 26

[1]	Boyd, D. R.; Sharma, N. D.; Loke, P. L.; Malone, J. F.; McRoberts, W. C.; Hamilton, J. T. Org. Biomol. Chem. 2007, 5, 2983.
[2]	(a) Sun, N.; Du, R. L.; Zheng, Y. Y.; Huang, B. H.; Guo, Q.; Zhang, R. F.; Wong, K. Y.; Lu, Y. J. Eur. J. Med. Chem. 2017, 135, 1. pmid: 27983846
	(b) Zablotskaya, A.; Segal, I.; Geronikaki, A.; Shestakova, I.; Nikolajeva, V.; Makarenkova, G. Pharmacol. Rep. 2017, 69, 575. doi: S1734-1140(16)30130-X pmid: 27983846
	(c) Nathubhai, A.; Haikarainen, T.; Koivunen, J.; Murthy, S.; Koumanov, F.; Lloyd, M. D.; Holman, G. D.; Pihlajaniemi, T.; Tosh, D.; Lehti, L. J. Med. Chem. 2017, 60, 814. doi: 10.1021/acs.jmedchem.6b01574 pmid: 27983846
	(d) Murugavel, S.; Stephen, C. S. J. P.; Subashini, R.; AnanthaKrishnan, D. J. Photochem. Photobiol. B 2017, 173, 216. pmid: 27983846
	(e) Keri, R. S.; Patil, S. A. Biomed. Pharmacother. 2014, 68, 1161. pmid: 27983846
	(f) García, E.; Coa, J. C.; Otero, E.; Carda, M.; Vélez, I. D.; Robledo, S. M.; Cardona, W. I. Med. Chem. Res. 2018, 27, 497. pmid: 27983846
	(g) Fouda, A. M. Med. Chem. Res. 2017, 26, 302. pmid: 27983846
	(h) Pinz, M. P.; Reis, A. S.; Leivas, R.; Voss, G. T.; Wilhelm, E. A. Regul. Toxicol. Pharm. 2017, 90, 72. pmid: 27983846
[3]	(a) Aly, M.; Ibrahim, M. M.; Okael, A.; Gherbawy, Y. Russ. J. Bioorg. Chem. 2014, 40, 214.
	(b) Chen, R.; Yang, X.; Tian, H.; Sun, L. J. Photochem. Photobiol. A: Chem. 2007, 189, 295.
	(c) Song, S.; Zhao, W.; Wang, L.; Redshaw, C.; Wang, F.; Sun, W. J. Organomet. Chem. 2011, 696, 3029.
[4]	(a) Denmark, S. E.; Venkatraman, S. J. Org. Chem. 2006, 71, 1668. pmid: 16468822
	(b) Waldvogel, S. R. Adv. Synth. Catal. 2004, 345, 91. pmid: 16468822
	(c) Li, X.; Mao, Z.; Wang, Y.; Chen, W.; Lin, X. Tetrahedron 2011, 67, 3858. pmid: 16468822
	(d) Wang, L. M.; Hu, L.; Chen, H. J.; Sui, Y. Y.; Shen, W. ChemInform 2009, 40, 406. pmid: 16468822
	(e) Brouet, J. C.; Gu, S.; Peet, N. P.; Williams, J. D. ChemInform 2009, 39, 1563. pmid: 16468822
	(f) Bharate, J. B.; Vishwakarma, R. A.; Bharate, S. B. Rsc. Adv. 2015, 5, 42020. pmid: 16468822
	(g) Cadamuro, B. S. Tetrahedron Lett. 2010, 51, 2342. pmid: 16468822
[5]	Wang, L.; Shen, Q.; Yu, J. J.; Liu, M. T.; Qiu, J.; Fang, L.; Guo, F. L.; Tang, J. Synthesis 2012, 44, 389.
[6]	Marco-Contelles, J.; Pérez-Mayoral, E.; Samadi, A.; Carreiras, M. C.; Soriano, E. Chem. Rev. 2009, 109, 2652. doi: 10.1021/cr800482c pmid: 19361199
[7]	(a) Singh, V. K.; Donthireddy, S. N. R.; Pandey, V. K.; Rit, A. Org. Biomol. Chem. 2022, 20, 1945. pmid: 30047973
	(b) Sundarraman, B.; Rengan, R.; Semeril, D. Organometallics 2022, 41, 1314. pmid: 30047973
	(c) Xiong, B.; Wang, Y. Y.; Liu, Y.; Bao, Y. D.; Liu, Z. G.; Zhang, Y. N.; Liu, Y. Org. Biomol. Chem. 2018, 16, 5707. doi: 10.1039/c8ob01321g pmid: 30047973
	(d) Xu, J. X.; Chen, Q. M.; Luo, Z. G.; Tang, X. D.; Zhao, J. W. RSC Adv. 2019, 9, 28764. pmid: 30047973
	(e) Sk, M.; Bera, A.; Banerjee, D. ChemCatChem 2023, 15, 1. pmid: 30047973
[8]	Cini, E.; Petricci, E.; Truglio, G. I.; Vecchio, M.; Taddei, M. ChemInform 2016, 47, 31386.
[9]	Liu, X.; Liu, X.; Bi, Y.; Ke, J. Energ. Fuel. 2022, 36, 13238.
[10]	Chen, W. D.; Wu, X. Adsorpt. Sci. Technol. 2018, 36, 3.
[11]	Varma, R. S.; Saini, R. K.; Dahiya, R. Tetrahedron Lett. 1997, 38, 7823.
[12]	Lu, J. Q.; Zeng, J.; Abulikemu, A. R. Chin. J. Org. Chem. 2020, 40, 2483 (in Chinese).
	( 吕进强, 曾竟, 阿布都热西提•阿布力克木, 有机化学, 2020, 40, 2483.)
[13]	Pant, P. L.; Sonune, R. K.; Shankarling, G. S. ChemistrySelect 2018, 3, 5249.
[14]	Kalla, R. M. N.; Zhang, Y.; Kim, Ⅱ. New J. Chem. 2017, 41, 5373.
[15]	Anand, N.; Koley, S.; Ramulu, B. J.; Singh, M. S. Org. Biomol. Chem. 2015, 13, 9570.
[16]	Choudhury, S. S.; Jena, S.; Sahoo, D. K.; Shekh, S.; Kar, R. K.; Dhakad, A.; Gowd, K. H.; Biswal, H. S. ACS Omega 2021, 6, 19304.
[17]	Rajawinslin, R. R.; Gawande, S. D.; Kavala, V.; Huang, Y. H.; Kuo, C. W.; Kuo, T. S.; Chen, M. L.; He, C. H.; Yao, C. F. RSC Adv. 2014, 4, 37806.
[18]	Marina, G. O.; Antonio, J. L. P.; Rosa, M. M. A.; Jacek, P.; Elena, P. M.; Elena, S. ChemCatChem 2014, 6, 3440.
[19]	Sergey, V.; Elena, V. V.; Konstantin, L. Ivanov.; Ekaterina, M. B.; Mikhail, Y. M. Eur. J. Org. Chem. 2017, 19, 2814.
[20]	Kaewmee, B.; Rukachaisirikul, V.; Kaeobamrung, J. Org. Biomol. Chem. 2017, 15, 7387
[21]	Anderson, E. C.; Sneddon, H. F.; Hayes, C. J. Green Chem. 2019, 21, 3050. doi: 10.1039/c9gc00408d
[22]	Kishore, P. S.; Gujjarappa, R.; Putta, R. K.; Polina, S.; Singh, V.; Malakar, C. C.; Pujar, P. P. ChemistrySelect 2022, 7, 1.
[23]	Zhang, S. L.; Deng, Z. Q. Org. Biomol. Chem. 2016, 14, 8966.
[24]	Qu, F.; He, P.; Hu, R. F.; Cheng, X. H.; Wang, S.; Wu, J. Synth. Commun. 2015, 45, 2802.
[25]	Xu, J. X.; Pan, N. L.; Chen, J. X.; Zhao, J. W. J. Org. Chem. 2021, 86, 10747.
[26]	Cao, F.; Mao, A. R.; Yang, B. B.; Ge, C. Y.; Wang, D. W. New J. Chem. 2021, 45, 6768.