W-Nitrobenzaldehyde

Less satisfactory yields are obtained when the reaction is moderated by the addition of the w-nitrobenzaldehyde in several portions. 

In the preparation from w-nitrobenzaldehyde, sodium acetate, and acetic anhydride,2 no yield is mentioned in the literature. 

The reaction between equimolar quantities of hydrazoic acid and aldehydes in the presence of strong mineral acid yields nitriles and, to a lesser extent, N-substituted formyl derivatives, RNHCHO (Schmidt reaction). A number of aldehydes, including acetaldehyde, benzaldehyde, w-nitrobenzaldehyde, and vanillin, have been converted to the nitriles in yields of 64% to 83%. ... 

A SOLUTION of 450 g. (2 moles) of stannous chloride crystals (Note i) in 600 cc. of concentrated hydrochloric acid is placed in a 3-I. beaker provided with an efficient mechanical stirrer and cooled in an ice bath. When the temperature of the solution has fallen to +5 , 100 g. (0.66 mole) of w-nitrobenzaldehyde (Note 2) is added in one portion. The temperature rises slowly at first, reaching 25-30° in about five minutes, then rises very rapidly to about 100°. Stirring must be vigorous or the reaction mixture may be forced out of the beaker (Note 3). During the reaction the nitrobenzaldehyde dissolves, and an almost clear, red solution is obtained. The solution is cooled in an ice-salt mixture until the temperature has fallen to about -1-2°. During the cooling, orange-red crystals separate, and a pasty suspension results. 

Prepared by treating w-nitrobenzaldehyde with a methylmagnesium halide and oxidizing the resulting carbinol with chromic acid. Berungozzi, Atti accad. Lincei 19. 332 (i934) [C. A. 28, 5053 (i934)l-... 

A mixture of 75 gm of w-nitrobenzaldehyde, 98 gm of propionic anhydride, and 48 gm of sodium propionate is heated at 170°C in an oil bath for 5 hr. The reaction mixture is poured into water and saturated sodium carbonate solution added to strong alkalinity. The tarry liquid is boiled with decolorizing charcoal for 10 min and then filtered. The alkaline mixture is poured into dilute hydrochloric acid. 

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