Tributyltin Chloride → Tributyl-[4-methyl-2-(3-pyridyl)thiazol-5-yl]stannane

In a dry flask under argon, 5-bromo-4-methyl-2-(3-pyridyl)thiazole (15.00 g, 55.85 mmol) was dissolved in THF (140 mL), and with cooling to keep the temperature at 25°-30° C., treated dropwise with i-PrMgCl.LiCl (TurboGrignard, 60 mL, 78.19 mmol,). The resulting mixture was allowed to stir at ambient temperature for 1 hour. The reaction mixture was then cooled to 10° C., and tri-n-butyl tin chloride (19 mL, 67.02 mmol) was added over 5 min. The reaction was stirred for 30 min at ambient temperature and then at reflux (66° C.) for 18 hours. The reaction mixture was quenched with saturated NH4Cl solution and diluted with ethyl acetate. Then aqueous layer was extracted 3 times with ethyl acetate and the combined organic layers washed with brine, dried over MgSO4, filtrated and evaporated. Purification by Combi flash chromatography with a column of 24 g and a gradient cyclohexane: 0-100% ethyl acetate to give the title compound as a yellow solid (9.17 g, 26%).

1. temperaturewith cooling
2. customat 25°-30° C.
3. temperatureThe reaction mixture was then cooled to 10° C.
4. stirringThe reaction was stirred for 30 min at ambient temperature
5. temperatureat reflux (66° C.) for 18 hours
6. customThe reaction mixture was quenched with saturated NH4Cl solution
7. additiondiluted with ethyl acetate
8. extractionThen aqueous layer was extracted 3 times with ethyl acetate
9. washthe combined organic layers washed with brine
10. dry with materialdried over MgSO4
11. filtrationfiltrated
12. customevaporated
13. customPurification by Combi flash chromatography with a column of 24 g

ORD record

ord-8d5e8e29562249fcbcd40327bed7b429

Source dataset

uspto-grants-2015_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09133218B2