Mechanosynthesis of Fullerotetrahydroquinolines by Copper-Mediated sp³ C–H Functionalization of N,N-Dimethylanilines with [60]Fullerene

Abstract

An efficient mechanochemical copper-mediated coupling reaction of [60]fullerene with para- or meta-substituted N,N-dimethylanilines under solvent-free and ambient conditions has been developed. The present protocol provides N-methylfullerotetrahydroquinolines containing electron-withdrawing or electron-donating groups on the phenyl ring in a short reaction time and at room temperature. This reaction occurs through copper-mediated sp³ C–H functionalization of N,N-dimethylanilines under ball-milling conditions. In addition, a representative fullerotetrahydroquinoline has been applied in a perovskite solar cell device.

Key words

fullerenes - mechanochemistry - green chemistry - radical reaction - copper catalysis - solar cell

Publication History

Received: 20 June 2023

Accepted after revision: 24 July 2023

Accepted Manuscript online:
24 July 2023

Article published online:
07 September 2023

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• 15 Reaction of C₆₀ with N,N-Dimethylanilines 1a–q; General Procedure A mixture of C₆₀ (0.05 mmol), the appropriate 1 (0.075 mmol), and Cu(OTf)₂ (0.10 mmol), together with four stainless-steel balls (5 mm diameter), were introduced into a stainless-steel jar (5 mL) and milled vigorously (40 Hz) in a GT600 mixer mill at r.t. for 1 h. The mixture was then extracted with CS₂ and separated by column chromatography (silica gel, CS₂) to remove unreacted C₆₀; further elution with CH₂Cl₂–CS₂ (1:2) afforded product 2. 2a Prepared by the general procedure from C₆₀ (35.8 mg, 0.05 mmol), 1a (12.7 mg, 0.075 mmol), and Cu(OTf)₂ (36.9 mg, 0.10 mmol) as an amorphous brown solid; yield: 17.9 mg (41%) [recovered C₆₀: 13.5 mg (38%)]. FTIR (KBr): 1599, 1585, 1504, 1334, 1308, 1290, 1107, 527 cm^–1. ¹H NMR (500 MHz, 1:1 CS₂–CDCl₂): δ = 9.29 (d, J = 2.5 Hz, 1 H), 8.34 (dd, J = 9.2 Hz, 2.5 Hz, 1 H), 7.24 (d, J = 9.2 Hz, 1 H), 4.84 (s, 2 H), 3.49 (s, 3 H). 13C NMR (126 MHz, 1:1 CS₂–CDCl₂): δ = (all 2 C unless indicated) 155.39, 153.68 (1 C, aryl C), 152.18, 146.71 (1 C), 146.59 (1 C), 145.43, 145.39, 145.18, 145.13, 144.69, 144.46, 144.45, 144.33, 144.31, 144.30, 143.98, 143.60, 143.56, 142.04, 141.59 (4 C), 141.09, 141.00, 140.96, 140.78, 140.60, 140.58, 139.34, 139.23 (1 C, aryl C) , 138.93, 135.44, 133.54, 126.20 (1 C, aryl C), 123.79 (1 C, aryl C), 123.62 (1 C, aryl C), 111.99 (1 C, aryl C), 67.16 [1 C, C(sp³) of C₆₀], 64.21 (1 C), 62.85 [1 C, C(sp³) of C₆₀], 39.08 (1 C). MALDI-TOF MS: m/z [M^–] calcd for C₆₈H₈N₂O₂: 884.0591; found: 884.0590. UV/Vis (CHCl₃): λ_max nm (log ε): 259 (5.06), 318 (4.64), 433 (3.61), 697 (2.61).