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Synlett 2022; 33(14): 1383-1390
DOI: 10.1055/a-1809-7768
DOI: 10.1055/a-1809-7768
cluster
Organic Chemistry in Thailand
Brønsted Acidic Ionic Liquid Catalyzed Three-Component Friedel–Crafts Reaction for the Synthesis of Unsymmetrical Triarylmethanes
This work was financially supported by a Research Grant from Burapha University through the National Research Council of Thailand (Grant no. 162/2561), the Office of National Higher Education Science Research and Innovation Policy Council (NXPO) (Grant no. BO5F630030), the Center of Excellence for Innovation in Chemistry (PERCH-CIC) and the Research Unit in Synthetic Compounds and Synthetic Analogues from Natural Products for Drug Discovery (RSND), Burapha University. Special thanks to Dr. Ron Beckett, Faculty of Science, Burapha University for his comments and proofreading the English manuscript.
Abstract
A convenient and practical method for the synthesis of unsymmetrical triarylmethanes was demonstrated through a one-pot three-component double Friedel–Crafts reaction of various aliphatic, aromatic, or heteroaromatic aldehydes with N,N-dialkylanilines and indoles by using a Brønsted acidic ionic liquid as the catalyst. This method was successfully applied under metal- and solvent-free conditions at 80 °C, affording the corresponding unsymmetrical triarylmethane products in moderate to high yields from a broad range of substrates. In addition, the mechanism of this reaction was studied by quantitative NMR analysis.
Key words
triarylmethanes - diarylmethylindoles - Friedel–Crafts reaction - Brønsted acid - ionic liquid - metal-free conditionsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1809-7768.
- Supporting Information
Publikationsverlauf
Eingereicht: 14. Februar 2022
Angenommen nach Revision: 28. März 2022
Accepted Manuscript online:
28. März 2022
Artikel online veröffentlicht:
15. Juni 2022
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- 10 {4-[1H-Indol-3-yl(4-nitrophenyl)methyl]phenyl}dimethylamine (4a), 3,3′-[(4-nitrophenyl)methylene]bis-1H-indole (5a), and 4,4′-[(4-Nitrophenyl)methylene]bis(N,N-dimethylaniline) (6a): Typical Procedure A mixture of [bsmim][NTf2] (10 mol%), 4-nitrobenzaldehyde (1a; 1.0 mmol), N,N-dimethylaniline (2a; 2.0 mmol), and indole (3a; 1.0 mmol) was stirred at 80 °C for 6.0 h.When the reaction was complete, the mixture was cooled to r.t. and the reaction was quenched with sat. aq NaHCO3. The mixture was extracted with EtOAc (3×10 mL) and the combined organic layer was dried (Na2SO4) and concentrated in a rotary evaporator. The crude product was purified by column chromatography (silica gel, 20% EtOAc–hexane) to give 4a, 5a, and 6a. 4a Yellow oil; yield: 299 mg (81%); Rf = 0.25 (20% EtOAc–hexane). 1H NMR (400 MHz, CDCl3): δ = 8.13 (d, J = 8.8 Hz, 2 H), 8.07 (br s, 1 H), 7.40 (d, J = 8.8 Hz, 2 H), 7.37 (d, J = 8.0 Hz, 1 H), 7.23–7.17 (m, 2 H), 7.08 (d, J = 8.8 Hz, 2 H), 7.02 (td, J = 7.2, 0.8 Hz, 1 H), 6.71 (d, J = 8.8 Hz, 2 H), 6.59 (d, J = 1.6 Hz, 1 H), 5.68 (s, 1 H), 2.95 (s, 6 H). 13C NMR (100 MHz, CDCl3): δ = 152.56, 149.36, 146.29, 136.71, 130.23, 129.64, 129.45, 126.61, 124.01, 123.47, 122.26, 119.59, 119.53, 118.98, 112.60, 111.18, 47.76, 40.55. 5a Yellow solid; yield: 30 mg (8%); mp 230–232 °C; Rf = 0.11 (20% EtOAc–hexane). 1H NMR (400 MHz, CDCl3): δ = 8.14 (d, J = 8.8 Hz, 2 H), 8.03 (br s, 2 H), 7.51 (d, J = 8.8 Hz, 2 H), 7.39 (d, J = 8.0 Hz, 2 H), 7.34 (d, J = 8.0 Hz, 2 H), 7.20 (td, J = 7.4, 1.2 Hz, 2 H), 7.03 (td, J = 7.6, 1.2 Hz, 2 H), 6.69 (dd, J = 2.4, 1.6 Hz, 2 H), 5.99 (s, 1 H). 13C NMR (100 MHz, CDCl3): δ = 152.06, 146.39, 136.71, 129.46, 126.58, 123.74, 123.47, 122.01, 119.38, 119.28, 117.78, 111.27, 40.16. 6a Yellow solid; yield: 38 mg (10%); mp 172–174 °C; Rf = 0.47 (20% EtOAc–hexane). 1H NMR (400 MHz, CDCl3): δ = 8.11 (d, J = 8.8 Hz, 2 H), 7.29 (d, J = 8.4 Hz, 2 H), 6.95 (d, J = 8.4 Hz, 4 H), 6.67 (d, J = 8.8 Hz, 4 H), 5.45 (s, 1 H), 2.93 (s, 12 H). 13C NMR (100 MHz, CDCl3): δ = 153.46, 149.23, 146.15, 130.91, 130.05, 129.81, 123.33, 112.52, 54.89, 40.55.
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