4-Methyl-3-nitrobenzophenone,

C1JH14CINO5 33369-28-7) see Zomepirac 2 -carboxy-4-chloro-3-nitrobenzophenone (C14H8CINO5 85-54-1) see Chlortalidone [6/ -[6a,7p(Z)]]-l-[[2-carboxy-7-[[[[2-(l,l-dimethyl-ethoxy)- ,l-dimethyl-2-oxoethoxy]imino)[2-[(triphcnyl-methyl)amino]-4-thiazolyl]acetylJamino]-8-oxo-5-thia-l-azabicyclo[4.2.0]oct-2-en-3-yl]methyl]pyridinium inner salt... 

The above procedure is essentially that of Ullmann and Bleier.2 2-Aminobenzophenone has also been prepared by reduction of 2-nitrobenzophenone,3 by the Hofmann reaction of the amide of o-benzoylbenzoic acid with sodium hypobromite,4 by the action of an excess of benzoyl chloride on aniline at 220°,6 and by hydrolysis of the acetyl derivative which is obtained by the action of phenylmagnesium bromide on 2-methyl-3,l,4-benzoxaz-4-one (from anthranilic acid and acetic anhydride).6 Various methods for the preparation of 2-aminobenzophenones have been summarized critically by Simpson, Atkinson, Schofield, and Stephenson.7... 

Problem 15.18 Prepare the following compounds from benzene, toluene, and alcohols of four or fewer C s (a) 2-methylpropanal (isobutyraldehyde), (b) p-chlorobenzaldehyde, (c) p-nitrobenzophenone (p-NOjCftH4COC,.H,), (d) benzyl methyl ketone, (e) p-methylbenzaldehyde. ... 

Lewis and his co-workers have reported three interrelated syntheses of acronycine 208 (81T209). In one synthesis, 2,6-dimethoxy-4-hydroxy-2 -nitrobenzophenone 250, obtained as a minor product from Friedel-Crafts acylation of 3,5-dimethoxyphenol with 2-nitrobenzoylchloride, was treated with 3-chloro-3-methylbut-l-yne under basic conditions. The resultant nitro compound 251 was reduced to the amine 252 with zinc. Upon reaction with sodium hydride in DMSO, this amine provided a mixture of de-N-methylisoacronycine 253 and de-N-methylacronycine 210. T>e-N-methylacronycine 210 was converted to acronycine 208 by methylation with methyl iodide (Scheme 42). 

The O-acetate of 3-methyl-5-nitrobenzophenone oxime on thermolysis at 165°C under reduced pressure (20 mm) yields 5-methyl-7-nitro-3-phenyl-indoxazene (78%).28 The 5-methyl-6-nitro isomer is prepared similarly. 

Analogous ring closure to give fluorenones is also possible 2-amino-4 -methyl-5-nitrobenzophenone gives 6-methyl-2-nitrofluorenone in 75% yield on diazotization and three hours warming at 50°.798 804... 

By heating together 4-ehloro-3-nitro benzophenone and ammonia at 125°C for 24 hours in the presence of sulfolane yields 4-amino-3-nitrobenzophenone. The resulting product on being treated with hydrochloric acid and hydrogenation with Pd-on-charcoal as a catalyst yields diaminobenzophenone hydrochloride. This on being treated with S-methyl thiourea in the presence of methyl chloroformate... 

Internal standard 3-hydroxy-4-methoxy-4 -methyl-5-nitrobenzophenone (27)... 

Preparation by oxidation of 7-methyl-6-nitro-2,3-diphenyl-benzofuran wi(h chromium trioxidein acetic acid, followed by saponification of the keto ester so formed—the 2-(benzoyloxy)-3-methyl-4-nitrobenzophenone— with sodium hydroxide in boiling dilute ethanol (70%) [590]. 

Preparation by demethylation of 2-chloro-2 -methoxy-5 -methyl-4-nitrobenzophenone with excess boiling pyridinium chloride for 30 min (57%) [1073], m.p. 130° [1073] Spectra (NA). 

Preparation by deethylation of 2-ethoxy-5-methyl-4 -nitrobenzophenone (SM) in the presence of aluminium chloride in carbon disulfide at 60-70° for 8 h [141,619] according to [139]. SM was obtained by reaction of p-nitrobenzoyl chloride with p-methylphenetole in the presence of aluminium chloride. 

Also obtained by adding aqueous ammonia to a mixture of 2-hydroxy-5-methyl-3 -nitrobenzophenone and ferrous sulfate in aqueous ethanol at 80-85°, isolation of the amino compound, then treattnent with 2 N hydrochloric acid (33%) [919]. 

Also obtained by reduction of 2-methoxy-5-methyl-4 -nitrobenzophenone (m.p. 101-102°) [683],... 

Preparation by demethylation of 2,5-dimethoxy-2 -methyl-3 -nitrobenzophenone (SM) with boron tribromide in methylene chloride at 0° for 15-17 h (70-95%). SM was prepared by reaction of 2-methyl-3-nitrobenzoic acid with... 

Preparation by demethylation of 4-hydroxy-3-methoxy-2 -methyl-5-nitrobenzophenone with hydrobromic acid in refluxing aqueous acetic acid [1019],... 

---