Synlett 2022; 33(14): 1383-1390
cluster
Organic Chemistry in Thailand
Brønsted Acidic Ionic Liquid Catalyzed Three-Component Friedel–Crafts Reaction for the Synthesis of Unsymmetrical Triarylmethanes
Suttida Rinkam
a
Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Burapha University, Sangesook, Chonburi 20131, Thailand
,
Warapong Senapak
a
Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Burapha University, Sangesook, Chonburi 20131, Thailand
,
Sarayut Watchasit
c
Nuclear Magnetic Resonance Spectroscopic Laboratory, Science Innovation Facility, Faculty of Science, Burapha University, Chonburi 20131, Thailand
,
Rungnapha Saeeng
a
Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Burapha University, Sangesook, Chonburi 20131, Thailand
b
The Research Unit in Synthetic Compounds and Synthetic Analogues from Natural Product for Drug Discovery (RSND), Burapha University, Chonburi 20131, Thailand
,
a
Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Burapha University, Sangesook, Chonburi 20131, Thailand
b
The Research Unit in Synthetic Compounds and Synthetic Analogues from Natural Product for Drug Discovery (RSND), Burapha University, Chonburi 20131, Thailand
› Institutsangaben
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 conditions
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{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 (Na2 SO4 ) 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). 1 H 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). 13 C 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). 1 H 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). 13 C 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). 1 H 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). 13 C 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.
11
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