Tributylstannane → HCID 18980060, compound

Temperature

103 °C

Tris(dibenzylideneacetone)dipalladium (O) (0.12 g) in toluene (45 mL) was treated with tri-2-furyl phosphine (0.12 g) under argon. The solution was stirred for 15 minutes at low temperature and treated with methyl propiolate (1.15 mL, 1.09 g) followed by tri-n-butyltin hydride (3.50 mL, 3.78 g). The solution was stirred for 19 hours and then treated with more tris (dibenzylacetone) dipalladium (O) (0.10 g) and tri-2-furylphosphine (0.10 g). The mixture was stirred for 15 minutes and then treated with 8-chloro-4-iodo-3-methoxy-2,5-dioxo-2,5-dihydro-1H-benz[b]azepine (3.63 g) followed by toluene (35 mL). The mixture was heated to 103° C. and it was stirred for 19 hours. The mixture was cooled and concentrated to a dark solid. It was dissolved in chloroform and chromatographed on a silica gel column (8 cm diameter by 17 cm long) using 17% ethyl acetate in hexane to give a pale yellow solid (0.533 g). The solid was recrystallized twice from ethyl acetate (30 mL). The solution was concentrated to 10 mL volume and the crystals were filtered off, washed with cold ethyl acetate, washed with hexane to give a white solid (0.083 g); mp 260.1°-260.5° C. (dec); 1H NMR (CDCl3) 7.73 (d,1, J=16.1), 6.71 (d,1, J=16.1) for trans olefin protons; MS: m/z=322 (M+1). Analysis for C15H12ClNO5 : Calculated: C, 56.00; H, 3.76; N, 4.35; Found: C, 55.45; H, 3.85; N, 4.13.

1. stirringThe solution was stirred for 19 hours
2. stirringThe mixture was stirred for 15 minutes
3. stirringit was stirred for 19 hours
4. temperatureThe mixture was cooled
5. concentrationconcentrated to a dark solid
6. dissolutionIt was dissolved in chloroform
7. customchromatographed on a silica gel column (8 cm diameter by 17 cm long)

ORD record

ord-7053bde5916b4e6cb6bc23508d3fabf2

Source dataset

uspto-grants-1997_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05656626