Nitric Nitroacetophenone

Nitric acid, 48 o-Nitroacetophenone, 70 -Nitroacetophenone, T1 o-Nitrobenzoyl chloride, 70... 

No reference was given to a detailed paper by R. Camps, Arch. d. Pharm. 240, 1 (1902). This author adds the acetophenone to ten times its weight of fuming nitric acid at temperatures of —10 to +20°. At the lower temperature a 96 per cent yield of nitroacetophenones was obtained, consisting of 45 per cent of the ortho derivative and 55 per cent of the meta. 

The nitration of acetophenone has been extensively studied. It is carried out at a low temperature (5° to -20°) by the action of nitric and sulfuric acids and gives m-nitroacetophenone (55 83%) and smaller amounts of o-nitroacetophenone. Under similar conditions, benzalde-hyde is converted to m-nitrohenzaldehyde (84%). If nitration is performed on benzaldehyde diacetate, C(HsCH(CXZCXZH3)2, with subsequent hydrolysis, p-nitrobenzaldehyde (73%) is obtained furthermore, a slight modification of this procedure causes the formation of mainly the ortho isomer (43%). ... 

For acetophenone, only meta-nitration has preparative value. As for benz-aldehyde, this is favored by a large excess of concentrated or, better, fuming sulfuric acid and by reaction at as low a temperature as possible 209 yields of jw-nitroacetophenone exceeding 90% have been obtained in this way.210,211 Use of nitric acid alone or increase in the reaction temperature increases the amount of ortho-isomer formed,212 but this is nevertheless not a satisfactory method of synthesis. 

Acetophenone possesses the properties characteristic of aromatic compounds. When heated with dilute nitric acid it is oxidized to benzoic acid with concentrated nitric acid nitro derivatives are formed. The chief product of nitration is m-nitro-acetophenone a small proportion of the ortho compound is also formed. p-Nitroacetophenone can be prepared from p-nitro-benzoyl chloride and acetoacetic ester. 

---