Reaction of 2-Aminobenzyl Alcohols with β-Dicarbonyl Compounds to Synthesize Quinoline Derivatives in Water Promoted by Active Manganese Dioxide

doi:10.6023/cjoc202309009

Abstract

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

Cite this article

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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Fig. & Tab. 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

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