4-Bromopyridine → HCID 14171061, compound

Temperature

-70 °C

15.0 g. (0.095 mol) of 4-bromopyridine in 7 ml. of dry tetrahydrofuran (THF) was added dropwise at -70° C. to a solution of butyl lithium (1.6 M, 60.9 ml., 0.098 mol) dissolved in 120 ml. of dried THF over a ten minute period. The resulting very deep purple mixture was stirred at -70° C. for 30 minutes and then transferred by nylon tubing under positive nitrogen pressure into a stirred 0° C. solution of ethyl oxalate (55.2 g., 0.38 moles) in 90 ml. of dry THF. The solution was stirred at 0° C. for 45 minutes and then quenched by addition of 65 ml. glacial acetic acid. This was warmed to room temperature and poured into 500 ml. of water adjusted to pH 7.0 with saturated sodium bicarbonate and extracted with 3×200 ml. ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate filtered and concentrated to a brown oil. This oil was flash chromatographed on silica gel eluted with 1:2 ethyl acetate hexane. A viscous yellow oil was obtained; 5.8 g (34%), m/e 179, spectral data consistent with structure of title product.

1. dissolutiondissolved in 120 ml
2. custominto a stirred 0° C.
3. stirringThe solution was stirred at 0° C. for 45 minutes
4. customquenched by addition of 65 ml
5. temperatureThis was warmed to room temperature
6. additionpoured into 500 ml
7. extractionextracted with 3×200 ml
8. washThe combined organic layers were washed with brine
9. dry with materialdried over magnesium sulfate
10. filtrationfiltered
11. concentrationconcentrated to a brown oil
12. customchromatographed on silica gel
13. washeluted with 1:2 ethyl acetate hexane
14. customA viscous yellow oil was obtained

ORD record

ord-6b154f81add64277af401db1b41dd742

Source dataset

uspto-grants-1987_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04656169