Synthetic Route of 1435-44-5,Some common heterocyclic compound, 1435-44-5, name is 1-Chloro-2,4-difluorobenzene, molecular formula is C6H3ClF2, traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.
EXAMPLE 81 3-(2,4-Difluorophenylamino)-8-nitro-6H-dibenzo[b,e]oxepin-11-one (7) In accordance with general method Z, 0.50 g (1.85 mmol) of (6), 0.28 g (1.89 mmol) of 1-chloro-2,4-difluorobenzene, 2 spatula tips of Pd(OAc)2, 0.09 g of 2-(dicyclohexylphosphino)-2′,4′,6′-triisopropylbiphenyl (phosphine ligand), 0.50 g of KOt-Bu, 1.5 ml of t-BuOH are weighed out and dissolved in 10 ml of toluene (anhydrous). The mixture is refluxed at 100 C. under an argon atmosphere for 4 h. The crude product is purified by chromatography over silica gel with MC/EtOH (98/2). Yield: 0.05 g (7.0%); melting point: 210-214 C. C20H12F2N2O4 (Mr=382.33); LC 8.97 min 1H-NMR (DMSO-d6) delta in ppm: 8.84 (s, 1H, aryl H), 8.48 (d, 1H, J=2.01 Hz, aryl H), 8.30 (m, 1H, aryl H), 8.01 (dd, 2H, J1=2.70 Hz, J2=3.25 Hz, aryl H), 7.47-7.33 (m, 2H, aryl H), 7.15-7.04 (m, 2H, aryl H), 6.63 (d, 1H, J=10.0 Hz, aryl H), 6.24 (s, 1H, aryl H), 5.34 (s, 2H, -CH2-O) 13C-NMR (DMSO-d6) in ppm: 186.11 (C11), 163.30 (C4a), not detected (C4′, C2′), 152.89 (C8), 149.52 (C3), 145.34 (C6a), 137.76 (C10a), 133.85 (C1), 131.01 (C10), 127.38 (C1′, J=9.85 Hz), 124.23 (C6′, J=14.23 Hz), 116.52 (C7), 112.57 (C5′, J=3.52 Hz), 110.35 (C2), 105.45 (C3′, J=24.29 Hz), 101.93 (C4), 72.03 (C6) IR (ATR) (cm-1): 2849, 1643, 1608, 1531, 1297, 1249, 1150, 740 MS (ESI) 381.1 [M-H]-. General Method ZThe stated amounts of 3-amino-8-nitro-6H-dibenzo[b,e]oxepin-11-one, phosphine ligand, KOt-Bu, tert-butanol, haloaromatic, Pd(OAc)2 are weighed into a dry 100 ml three-necked flask with a reflux condenser, bubble counter and thermometer. The mixture is suspended in toluene (anhydrous) under an argon atmosphere and the suspension is heated to 110 C. and refluxed for 2 h. Hydrolysis with ice-water and repeated extraction with EtOAc are carried out. The combined organic phases are filtered and then concentrated in vacuo. The residue is purified by chromatography.
The synthetic route of 1435-44-5 has been constantly updated, and we look forward to future research findings.
Reference:
Patent; Laufer, Stefan; Albrecht, Wolfgang; US2012/115862; (2012); A1;,
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