3- Benzoyl-4- cinnoline

Both 4-nitrocinnoline 1-oxide and the 5-nitro isomer give 4,5-dinitrocinnoline 1-oxide when treated with fuming nitric and sulfuric acids. Cinnoline 1-oxide also reacts with benzoyl chloride/silver nitrate to give 3-nitrocinnoline 1-oxide in 71% yield. 

Nitration of cinnoline 2-oxide takes a different course. With nitric and sulfuric acids or with potassium nitrate and sulfuric acid a mixture of 8-nitrocinnoline 2-oxide, 6-nitrocinno-line 2-oxide and 5-nitrocinnoline 2-oxide is obtained, while with benzoyl nitrate in chloroform only a low yield (1.5%) of the 5-nitro derivative is obtained. 

In ether solutions in the absence of air, benzo[c]cinnoline forms adducts with alkali metals containing two atoms of the metal. These give solutions of 6 on treatment with benzoic acid or other source of protons. When one equivalent of benzo[c]cinnoline is added to the violet solution of the disodium derivative (50), an equilibrium is set up and the dark green sodium derivative of the radical anion (52) precipitates [Eq. (13)]. Reaction of the dilithium adduct (51) with one equivalent of benzoyl chloride results in disproportionation into benzo[c]cinnoline and, after hydrolysis, 2,2 -dibenzamidobiphenyl [Eq. (14)]. Methylation of the dilithium derivative... 

Methoxy-2-(3,3-tetramethylenetriazeno)acetophenone (32) was converted into the sodium salt of ethyl 2-[4-methoxy-2-(3,3-tetramethylenetriaz-l-eno)benzoyl] acetate (33) [NaH, OC(OEt)2, THF, reflux substrate during 8h crude] and thence into ethyl 7-methoxy-4-oxo-l,4-dihydro-3-cinnoline-carboxylate (34) with loss of pyrrolidine (neat F3CCO2H, 0°C, 12 h 83% overall). ... 

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