Potassium Carbonate → 2-(3-nitropyridin-2-yl)acetonitrile

Using the procedure of R. B. Katz, M. Voyle, Synthesis, 314-316 (1989), a mixture of 2-chloro-3-nitro-pyridine (9.51 g, 60 mmol), K2CO3 (20.7 g, 150 mmol) and t-butyl cyanoacetate (13.0 mL, 90 mmol) in THF is heated at reflux temperature for 24 h, cooled and concentrated in vacuo. The residue is suspended in 1:1 water/CH2Cl2 and carefully acidified to pH 1 with concentrated hydrochloric acid. The layers are separated and the organic layer is dried over MgSO4 and concentrated in vacuo to a dark oil. This oil is treated with p-toluene-sulfonic acid monohydrate (1.0 g) and toluene, heated at reflux temperature for 2 h, cooled and decanted. The dark residue is washed with CH2Cl2. The combined CH2Cl2 washes and toluene superinnate are washed with saturated aqueous NaHCO3, dried over MgSO4 and concentrated in vacuo to an oily solid. Trituration with 20:80 ethyl acetate:hexanes gives the title compound as an orange-brown solid, 6.50 g, (66% yield), mp 106-108° C., identified by NMR and mass spectral analyses.

1. customVoyle, Synthesis, 314-316 (1989)
2. temperatureis heated
3. temperatureat reflux temperature for 24 h
4. temperaturecooled
5. concentrationconcentrated in vacuo
6. customThe layers are separated
7. dry with materialthe organic layer is dried over MgSO4
8. concentrationconcentrated in vacuo to a dark oil
9. additionThis oil is treated with p-toluene-sulfonic acid monohydrate (1.0 g) and toluene
10. temperatureheated
11. temperatureat reflux temperature for 2 h
12. temperaturecooled
13. customdecanted
14. washThe dark residue is washed with CH2Cl2
15. washThe combined CH2Cl2 washes and toluene superinnate are washed with saturated aqueous NaHCO3
16. dry with materialdried over MgSO4
17. concentrationconcentrated in vacuo to an oily solid

ORD record

ord-f67f5010498041999662b803d114edd6

Source dataset

uspto-grants-2009_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07585876B2