O Nitroacetophenone

Formic acid is a good reducing agent in the presence of Pd on carbon as a catalyst. Aromatic nitro compounds are reduced to aniline with formic acid[100]. Selective reduction of one nitro group in 2,4-dinitrotoluene (112) with triethylammonium formate is possible[101]. o-Nitroacetophenone (113) is first reduced to o-aminoacetophenone, then to o-ethylaniline when an excess of formate is used[102]. Ammonium and potassium formate are also used for the reduction of aliphatic and aromatic nitro compounds. Pd on carbon is a good catalyst[103,104]. NaBH4 is also used for the Pd-catalyzed reduction of nitro compounds 105]. However, the ,/)-unsaturated nitroalkene 114 is partially reduced to the oxime 115 with ammonium formate[106]... 

This procedure is an adaptation of one described by Walker and Hauser. Schofield and Swain state that, in their opinion, for both convenience and economy, this method is the best yet described for the preparation of o-nitroacetophenone. ... 

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

To the crude diethyl o-nitrobenzoylmalonate is added a solution of 60 ml. of glacial acetic acid, 7.6 ml. of concentrated sulfuric acid, and 40 ml. of water, and the mixture is heated under reflux for 4 hours (Note 4) or until no more carbon dioxide is evolved. The reaction mixture is chilled in an ice bath, made alkaline with 20% sodium hydroxide solution, and extracted with several portions of ether. The combined ethereal extracts are washed with water and dried with anhydrous sodium sulfate followed by Drierite, and the solvent is removed by distillation. On fractional distillation of the residue, 27.0-27.4 g. (82-83%) of light-yellow o-nitroacetophenone boiling at 158-159°/16 mm. is obtained n 1.548, wg 1.551, df 1.236) (Note 5). 

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%). ... 

Anthranil and its 3-methyl derivative are obtained by electrolytic reduction of o-nitrobenzaldehyde and o-nitroacetophenone, respectively.133 In each case the anthranils are characterized as their HgCl2 complexes. 

Dimethylamine hydrodiloride dissolved in aq. 40%-formaldehyde soln., after 0.5 hr. acetic anhydride added, warmed with shaking until a gently refluxing clear soln. results, o-nitroacetophenone added, and heated 0.5 hr. on a water bath -> o-nitro- -dimethylaminopropiophenone. Y 64.2%. - This procedure minimizes reaction of the product with the remaining formaldehyde. F. e. s. W. Back, Ardi. Pharm. 303, 491 (1970). 

Acetophenone, methyl-/7-tolyl ketone p-chloroacetophenone, /7-bromoaceto-phenone, methyl -anisyl ketone, 2,4-di-methoxyacetophenone,2-methyl-4-metho-xyacetophenone, 5-methyl-2-methoxyace-tophenone, acetocumene, 2,5-trimethyl-acetophenone, 0-, m-, p-hydroxyaceto-phenone, 2,4-dihydroxyacetophenone, 3-methoxy-4-hydroxyacetophenone, o-nitroacetophenone, m-nitroacetopheno-ne, /7-nitroacetophenone, o-, m-, /7-ami-noacetophenone, 2-aceto-l -naphthoxy-acetic acid, 2-aceto-4-bromo-l-naphtho-xyacetic acid... 

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