Synlett 2018; 29(07): 979-985
DOI: 10.1055/s-0037-1609200
letter
© Georg Thieme Verlag Stuttgart · New York

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

Dewal S. Deshmukh
Department of Chemistry, Institute of Chemical Technology, Matunga, Mumbai-400019, India   Email: bm.bhanage@ictmumbai.edu.in
,
Department of Chemistry, Institute of Chemical Technology, Matunga, Mumbai-400019, India   Email: bm.bhanage@ictmumbai.edu.in
› Author Affiliations
D.S.D. thanks the University Grant Comission (UGC), New Delhi, India for providing a Senior Research Fellowship under Basic Science ­Research (BSR) scheme [F.25-1/2014-15(BSR)/F.7-227/2009 (BSR), 16th Feb 2015].
Further Information

Publication History

Received: 27 October 2017

Accepted after revision: 18 December 2017

Publication Date:
29 January 2018 (online)


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.

Supporting Information

 
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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)