Benzene, 1-bromo-3-iodo- → ((3-Bromophenyl)ethynyl)trimethylsilane

To a solution of m-bromoiodobenzene (25.0 g. 881.1 mmol) in diisopropylamine (500 ml), there were added bis(triphenylphosphine)palladium dichloride (1.24 g. 1.80 mmol) and copper (I) iodide (1.24 g, 2.03 mmol). The solution was degassed via a rapid stream of argon, and trimethylsilylacetylene (9.51 g, 97.0 mmol) was added over a period of 15 min. The reaction mixture was stirred at room temperature until G.C. analysis indicated the disappearance of starting material (2 h). The reaction mixture was cooled to room temperature and filtered to remove salts. The filtrate was concentrated in vacuo, and the oily residue was taken up in dichloromethane. The solution was washed with an aqueous 5% HCl solution (2×200 ml), water (2×200 ml) and brine (1×200 ml). The combined organic layers were dried (MgSO4) and the solvent removed in vacuo yielding the crude product as a yellow oil. The liquid chromatographed from silica gel in pentane. Elution with pentane gave the product (1b) (20.59 g, 91%) as a clear liquid: bp 81°-82° C., 1H NMR (200 MHz, CDCl3) c 0.30 (s), 7.23(m).

1. additionwas added over a period of 15 min
2. customthe disappearance of starting material (2 h)
3. temperatureThe reaction mixture was cooled to room temperature
4. filtrationfiltered
5. customto remove salts
6. concentrationThe filtrate was concentrated in vacuo
7. washThe solution was washed with an aqueous 5% HCl solution (2×200 ml), water (2×200 ml) and brine (1×200 ml)
8. dry with materialThe combined organic layers were dried (MgSO4)
9. customthe solvent removed in vacuo
10. customyielding the crude product as a yellow oil
11. customThe liquid chromatographed from silica gel in pentane
12. washElution with pentane

ORDレコード

ord-f4c74cf4c1a64b56a5c4629dad152d89

出典データセット

uspto-grants-1997_07

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US05645809