4-Chloro-3-nitrobenzophenone

Reaction of 4-chloro-4 -nitrobenzophenone with phenylacetonit riles... 

A model depicting a variety of reactions is 4-chloro-4-nitrobenzophenon (X). It contains four possible positions of attack ... 

Amino-5-bromophenyl(pyridin-2-yl)methanone ( ABP , deep violet, hR < 5), 2-amino-5-nitrobenzophenone ( ANB , pink, hR 15 — 20), 2-amino-5-chloro-... 

The following description is taken from U.S. Patent 3,116,203. A stirred solution of 75 g of 2-amino.2 -nitrobenzophenone in 700 ml of hot concentrated hydrochloric acid was cooled to 0°C and a solution of 21.5 g of sodium nitrite in 50 ml of water was added in the course of 3 hours. The temperature of the suspension was kept at 2° to 7°C during the addition. The resulting clear solution was poured into a stirred solution of 37 g of cuprous chloride in 350 ml of hydrochloric acid 1 1. The solid which had formed after a few minutes was filtered off, washed with water and recrystallized from ethanol. Crystals of 2-chloro-2 -nitrobenzophenone melting at 76° to 79°C were obtained. 

A solution of 20 g of 2-chloro-2. nitrobenzophenone in 450 ml of ethanol was hydrogenated at normal pressure and room temperature with Raney nickel. After uptake of about 6 liters of hydrogen the catalyst was filtered off, and the alcohol then removed in vacuo. The residue was distilled in a bulb tube at 0.4 mm and a bath temperature of 150° to 165°C giving a yellow oil. The oil was dissolved in alcohol, and on addition of water, needles of 2.amino.2. chlorobenzophenone melting at 58° to 60°C were obtained. 

A mixture of 5.2 parts of 4-chloro-3-nitrobenzophenone, 5 parts of ammonia, 72 parts of methanol and 13 parts of sulfolane is heated overnight at 125°C in a sealed tube. The reaction mixture is evaporated in vacuo. The semisolld residue is boiled in 100 parts of a diluted hydrochloric acid solution. After cooling, the precipitated product Is filtered off and dissolved in chloroform. The chloroform phase is dried and evaporated. The residue is crystallized from toluene, yielding 4-amino-3-nitrobenzophenone MP 141°C. 

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... 

C7H4CINO4 99-60-5) see Ethacridine 2-chloro-2 -nitrobenzophenone (C HjClNO, 2894-44-2) see Clonazepam... 

The reduction of a dinitro ketone to an azo ketone is best achieved with glucose. 2,2 -Dinitrobenzophenone treated with glucose in methanolic sodium hydroxide at 60° afforded 82% of dibenzo[c,f [i 2]diazepin-l 1-one whereas lithium aluminum hydride yielded 24% of bis(o-nitrophenyl)methanol [575], Conversion of aromatic nitro ketones with a nitro group in the ring into amino ketones has been achieved by means of stannous chloride, which reduced 4-chloro-3-nitroacetophenone to 3-amino-4-chloroacetophenone in 91% yield [178]. A more dependable reagent for this purpose proved to be iron which, in acidic medium, reduced m-nitroacetophenone to m-aminoacetophenone in 80% yield and o-nitrobenzophenone to o-aminobenzophenone in 89% yield (stannous chloride was unsuccessful in the latter case) [903]. Iron has also been used for the reduction of o-nitrochalcone, 3-(o-nitrophenyl)-l-phenyl-2-propen-l-one, to 3-(o-aminophenyl)-l-phenyl-2-propen-l-one in 80% yield [555]. 

Nitrobenzophenone, 32, 12 o-Nitrobenzoyl chloride, 30, 70 o-Nitrochlorobenzene, 32, 24 9-Nitro-10-chloro-9,10-dihydroanthra-... 

Condensation of 3-chloro-3-methylbutyne with 2,6-dimethoxy-7-hydroxy-2-nitrobenzophenone ... 

To a stirred and cooled (ice bath) suspension of 25 parts of aluminum chloride in 52 parts of fluorobenzene is added dropwise a solution of 27.5 parts of 4-chloro-3-nitrobenzoyl chloride in 52 parts of fluorobenzene. Upon completion, stirring is continued overnight at room temperature. The reaction mixture is poured onto water and the product is extracted with methylene chloride. The extract is washed successively with sodium hydrogen carbonate solution and water, dried, filtered and evaporated in vacuo. The solid residue is crystallized from 2-propanol, yielding 4-chloro-4 -fluoro-3-nitrobenzophenone MP 97.9°C. 

A mixture of 24.5 parts of 4-chloro-4 -fluoro-3-nitrobenzophenone, 72 parts of methanol, 13 parts of sulfolane and 3.12 parts of ammonia is heated in a sealed tube for 20 hours at 120°C. To the reaction mixture is added successively 50 parts of water and 25 parts of a diluted hydrochloric acid solution and the whole is stirred and refluxed for 5 minutes. The reaction mixture is cooled and the precipitated product is filtered off. It is washed with... 

The pathway of the reaction of 2-chloro-5-nitrobenzophenone with excess N,N-dimethylhydrazine is rather interesting (Scheme 2.29). In this case l,3-dimethyl-5-nitroindazole is formed fast and in high yield [305],... 

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). 

A mixture of 24.5 parts of 4-chloro-4 -fluoro-3-nitrobenzophenone, 72 parts of methanol,... 

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