Pinacolone → Pentanenitrile, 4,4-dimethyl-3-oxo-

To a solution of pinacolone (100.16 g, 1 mol) in methanol (300 ml) is introduced gaseous chlorine (70.91 g, 1 mol) at 15-20° C. over a period of 1 hour. The reaction mixture is neutralized with a 48% solution of sodium hydroxide in methanol (285 ml) and then aqueous solution of sodium hydrogen carbonate (4.20 g) in that order. After dilution with methanol (40 ml), the resulting mixture is mixed with an aqueous solution (137 ml) of sodium cyanide (58.81 g, 1.2 mol) and refluxed for 1 hour. The methanol is evaporated under atmospheric pressure over a period of 1.5 hours. The residue is mixed with a 4% aqueous sodium hydroxide (650 g) solution and shaken with benzene (300 ml) to remove neutral material (10.78 g). Hydrochloric acid (35%) (92.60 g) is poured into said alkaline aqueous layer below 15° C., and the mixture is shaken with benzene (750 ml). The benzene layer is washed with water, then mixed with an aqueous solution (44 ml) of sodium hydrogen carbonate (0.66 g), and the benzene layer is evaporated under atmospheric pressure. A solution of the residue is adjusted to pH 7.0 by stirring with benzene (142 ml), water (30 ml) then 35% hydrochloric acid (0.37 g). The benzene layer is dried and concentrated to give cyanopinacolone (106.70 g) as crystals melting at 64° to 67° C. Yield is 85 %. The product contains only 0.09% of 2-hydroxy-2-t-butylsuccinonitrile as a contaminant.

1. temperaturerefluxed for 1 hour
2. customThe methanol is evaporated under atmospheric pressure over a period of 1.5 hours
3. additionThe residue is mixed with a 4% aqueous sodium hydroxide (650 g) solution
4. customto remove neutral material (10.78 g)
5. additionHydrochloric acid (35%) (92.60 g) is poured
6. customalkaline aqueous layer below 15° C.
7. stirringthe mixture is shaken with benzene (750 ml)
8. washThe benzene layer is washed with water
9. additionmixed with an aqueous solution (44 ml) of sodium hydrogen carbonate (0.66 g)
10. customthe benzene layer is evaporated under atmospheric pressure
11. stirringby stirring with benzene (142 ml), water (30 ml)
12. dry with materialThe benzene layer is dried
13. concentrationconcentrated

ORD record

ord-e22e4d7b2b40469cba3987e5f6069a00

Source dataset

uspto-grants-1980_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04186144