Ethanethiol → 5-(Ethylthio)pyridin-2-amine

Temperatur

110 °C

In a 100 mL round-bottomed flask, 5-bromo-2-(2,2,5,5-tetramethyl-1,2,5-azadisilolidin-1-yl)pyridine (519 mg, 1.65 mmol), ethanethiol (102 mg, 122 μl, 1.65 mmol), xantphos (47.6 mg, 82.3 μmol) and Hunig's base (425 mg, 575 μl, 3.29 mmol) were combined with dioxane (10.0 ml) to give a light yellow solution. Pd2(dba)3 (37.7 mg, 41.1 μmol) was added and the mixture was evacuated and filled with Argon. The reaction mixture was heated to 110° C. and stirred for 17 h under argon. The mixture was cooled to 25° C. and conc. in vacuo. The residue was partitioned between 1M HCl and ether. Separated and basified aqueous phase with 3M NaOH. The aqueous layer was extracted with EtOAc (2×125 mL). The organic layers were combined, washed with H2O (1×50 mL), sat NaCl (1×25 mL), dried over Na2SO4 and concentrated in vacuo to an orange oil. The oil was dried overnight at 25° C. under vacuum to give an orange gum that was used crude in the subsequent oxidation. (M+H)+=155 m/e.

1. customto give a light yellow solution
2. customthe mixture was evacuated
3. additionfilled with Argon
4. temperatureThe mixture was cooled to 25° C. and conc. in vacuo
5. customThe residue was partitioned between 1M HCl and ether
6. customSeparated
7. extractionThe aqueous layer was extracted with EtOAc (2×125 mL)
8. washwashed with H2O (1×50 mL)
9. dry with materialdried over Na2SO4
10. concentrationconcentrated in vacuo to an orange oil
11. customThe oil was dried overnight at 25° C. under vacuum
12. customto give an orange gum that

ORD-Eintrag

ord-719448bc9b944d71872a3d3dc7fc34ba

Quelldatensatz

uspto-grants-2013_07

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08481540B2