Molecular Iodine Catalysed Benzylic sp³ C–H Bond Amination for the Synthesis of 2-Arylquinazolines from 2-Aminobenzaldehydes, 2-Aminobenzophenones and 2-Aminobenzyl Alcohols

Abstract

Molecular iodine catalysed benzylic sp³ C–H bond amination has been developed for the synthesis of quinazolines from 2-aminobenzaldehydes and 2-aminobenzophenones with benzylamines. The use of oxygen as a green oxidant combined with the transition-metal-, additive- and solvent-free conditions makes the methodology economical and greener. The lack of aqueous work up also enhances the efficiency of this protocol. A series of 2-arylquinazolines was synthesised in good to excellent yields by using the developed protocol. 2-Amino­benzyl alcohols could also be employed to prepare the corresponding quinazoline derivatives.

Key words

transition-metal free - benzylic sp³ amination - 2-aryl­quinazoline - molecular iodine - oxygen

• References and Notes

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• 26 General experimental procedure for the synthesis of 2-arylquinazolines (3): An oven-dried 25 mL round-bottom flask was charged with 2-aminobenzaldehyde/2-aminobenzophenone (1, 0.5 mmol) or 2-aminobenzyl alcohol (4a, 0.5 mmol) with benzylamine (2, 1.5 mmol) and molecular iodine (10 mol%). The mixture was then stirred at 130 °C for 3–15 h under an oxygen atmosphere, and the progress of the reaction was monitored by TLC. Upon completion, the mixture was cooled to room temperature and the crude product was purified by column chromatography. 6-Chloro-2-(4-methoxyphenyl)quinazoline (3b) Yellow solid (88%); mp 168–170 °C; ¹H NMR (400 MHz, CDC₃): δ = 9.32 (s, 1 H), 8.54–8.52 (m, 2 H), 7.95 (d, J = 9.0 Hz, 1 H), 7.85 (d, J = 2.1 Hz, 1 H), 7.77 (dd, J = 9.0, 2.3 Hz, 1 H), 7.02 (d, J =8.4 Hz, 2 H), 3.88 (s, 3 H); ¹³C NMR (101 MHz, CDCl₃): δ = 162.0, 161.1, 159.4, 149.3, 135.0, 132.2, 130.2, 130.1, 125.8, 123.7, 114.0, 55.4; GCMS (EI, 70 eV): m/z (%) = 270 (100), 255 (24), 227 (14), 192 (10). 2,4-Diphenylquinazoline (3q) White solid (88%); mp 117–119 °C; ¹H NMR (500 MHz, CDCl₃): δ = 8.69 (d, J = 8.1 Hz, 2 H), 8.15 (d, J = 8.4 Hz, 1 H), 8.11 (d, J = 8.4 Hz, 1 H), 7.89–7.85 (m, 3 H), 7.60–7.58 (m, 3 H), 7.54–7.47 (m, 4 H); ¹³C NMR (125 MHz, CDCl₃): δ = 168.3, 160.2, 152.0, 138.2, 137.7, 133.5, 130.5, 130.2, 129.9, 129.2, 128.7, 128.5, 127.0, 121.7; GCMS (EI, 70 eV): m/z (%) = 282 (65), 281 (100), 203 (8), 178 (8), 151 (6), 141 (7), 77 (8)