C.H.N Propionitrile

M. N. Elinson, R. F. NasybuUin, G. I. Nikishin, C. R. Chim. 2013, 16, 789-794. Sodium acetate catalyzed tandem Knoevenagel-Michael multicomponent reaction of aldehydes, 2-pyrazolin-5-ones, and cyano-functionalized C-H acids facile and efficient way to 3-(5-hydroxypyrazol-4-yl)-3-aryl-propionitriles. 

Stirring and heating were continued for a total of 2 h after which the mixture was cooled, poured into water and extracted with ether. The combined ether extract was washed several times with 2 N sodium hydroxide to remove phenol, dried over anhydrous sodium sulfate, and evaporated. The residue was distilled under water-pump vacuum to give pure 2-(3-methoxy-phenoxy)-propionitrile, boiling point 152-154°C/13 mm. 

Fig. 2. Propionitrile yield as a function of time in the oxygen aided dehydration of N-ethyl formamide. T = 37D°C partial pressures form amide 6 torr, oxygen 15 ton (in He). Catalyst 170 mg liquid hourly space velocity 1.7 h-1 (contact time, account taken of the carrier gas 0.9s) (10).

Nitriles Unlikely to be detected except in the case of acetonitrile (CH3CN) and propionitrile (C2H5CN) M -H1 ion may appear (especially at higher pressures) M -1 peak is weak but detectable (R-CH=C=N ) base peak at m/e = 41 (CH2=C=N+H) McLafferty rearrangement possible loss of HCN in the case of cyanobenzenes... 

S)-l-Methyl-2-[(N-naphthylamino)methyl]pyrrolidine 80 (0.088 mmol) in propionitrile (1 mL) was added to a solution oftin(II) triflate (0.08 mmol, 20 mol%) in propionitrile (1 mL). The mixture was cooled to —78 °C and a mixture of silyl ketene acetal 79 (0.44 mmol) and an aldehyde (0.4 mmol) was then added slowly over 3 h. The mixture was further stirred for 2 h, then quenched with saturated aqueous NaHC03. After the usual work up the aldol-type adduct was isolated as the corresponding trimethylsilyl ether 92. 

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