3-methylbenzene-1,2-diamine

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Tolylene dicarbamate was obtained in the same manner as in Example 1, except that the reaction time in the carbamate-forming reaction was set to 10 hours and that 8 g of the decomposed diaminotoluene (second diaminotoluene) obtained in Preparation Example 2 was blended with 100 g of the first diaminotoluene in the mixing step. It was confirmed that tolylene dicarbamate was obtained at a yield of 98 mol % as the total amount of 2,4-bis(butoxycarbonylamino)toluene (2,4-tolylene dicarbamate) and 2,6-bis(butoxycarbonylamino)toluene (2,6-tolylene dicarbamate). The isomer ratio of the mixed diaminotoluene was 2,4-diaminotoluene/2,6-diaminotoluene=81.1/18.9 (molar ratio). forming reaction

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Tolylene dicarbamate was produced in the same manner as in Example 1, except that 27 g of the decomposed diaminotoluene (second diaminotoluene) obtained in Preparation Example 1 was blended with 100 g of the first diaminotoluene. It was confirmed that tolylene dicarbamate was obtained at a yield of 95 mol % as the total amount of 2,4-bis(butoxycarbonylamino)toluene (2,4-tolylene dicarbamate) and 2,6-bis(butoxycarbonylamino)toluene (2,6-tolylene dicarbamate). obtained in Preparation Example 1

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Tolylene dicarbamate was produced in the same manner as in Preparation Example 1, except that the mixed diaminotoluene was used in place of the first diaminotoluene. It was confirmed that tolylene dicarbamate was obtained at a yield of 95 mol % as the total amount of 2,4-bis(butoxycarbonylamino)toluene (2,4-tolylene dicarbamate) and 2,6-bis(butoxycarbonylamino)toluene (2,6-tolylene dicarbamate).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Then, this reaction may be carried out, for example, by charging the mixed diaminotoluene, urea and/or N-unsubstituted carbamic acid ester, alcohol, if necessary, a catalyst and a reaction solvent, in a reaction vessel under the above-described conditions, and stirring or mixing the charged mixture. Tolylene dicarbamate containing 2,4-tolylene dicarbamate and 2,6-tolylene dicarbamate is produced as a main product. Then, this reaction mixing the charged mixture

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: U.S. Pat. No. 6,005,143 discloses a process for the adiabatic hydrogenation of dinitrotoluene in a monolith catalyst employing nickel and palladium as the catalytic metals. A single phase dinitrotoluene/water mixture in the absence of solvent is cycled through the monolith catalyst under plug flow conditions for producing toluenediamine.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3-methyl-1,2-diaminobenzene (5.00 g, 40.9 mmol) in formic acid (25 mL) was heated at 105° C. for 2 h. The reaction mixture was allowed to cool and then concentrated ammonium hydroxide (50 mL) was added dropwise. The mixture was extracted with dichloromethane (2×100 mL). The extracts were washed with brine, dried (Na2SO4), treated with charcoal, filtered, and evaporated to dryness. The residue was triturated with cold ether, filtered, and washed with cold ether, ether/hexane (1:1), and hexane to give 4-methylbenzimidazole (3.85 g, 71%) as a yellow solid. to cool The mixture was extracted with dichloromethane (2×100 mL) The extracts were washed with brine dried (Na2SO4) treated with charcoal filtered evaporated to dryness The residue was triturated with cold ether filtered washed with cold ether, ether/hexane (1:1), and hexane

Conditions: temp:180.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,3-diaminotoluene (2.44 g, 20 mmol), (E)-cinnamic acid (2.96 g, 20 mmol) and polyphosphoric acid (10 g) was heated to 180° C. for 90 min. The hot mixture was poured into water (100 ml), basified with 50% aqueous solution of sodium hydroxide and extracted with dichloromethane (3×100 ml). The combined extracts were washed with water (100 ml) and brine (100 ml), dried (magnesium sulfate) and concentrated to dryness. Purification by column chromatography (silica gel, 300 g; n-hexane/ethyl acetate (7/3)) yielded 0.61 g (13%) of the titled compound as red solids. extracted with dichloromethane (3×100 ml) The combined extracts were washed with water (100 ml) and brine (100 ml) dried (magnesium sulfate) concentrated to dryness Purification by column chromatography (silica gel, 300 g; n-hexane/ethyl acetate (7/3))

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 3-methyl-1,2-benzenediamine (11.9 g) and formic acid (150 mL) was heated at 70° C. for 15 minutes. The solvent was removed under reduced pressure and the residual oil was stirred with water (100 mL) and sodium hydroxide solution (65 mL of 4.0 N) was added until the solution was just basic. The precipitate was filtered off, washed with water, and air dried to give 11.6 g (90%) of 4-methyl-1H-benzimidazole, mp 141°-145° C. The solvent was removed under reduced pressure was added until the solution The precipitate was filtered off washed with water, and air dried

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Methyl-6-nitroaniline (15.2 g, 0.1 mol) was dissolved by heating in ethanol (150 mL). The solution was cooled, 10% palladium on carbon (1.0 g) was added and the solution was hydrogenated (50 lb initial hydrogen pressure) until uptake of hydrogen ceased (1 hour). The catalyst was filtered off and the ethanol was removed under reduced pressure to give 11.9 g (98%) of 3-methyl-1,2-benzenediamine as a solid which was used without purification. The solution was cooled (1 hour) The catalyst was filtered off the ethanol was removed under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The 5-amino-5,6-dihydro-4H-imidazo(4,5,1-ij)quinolin-2-ones of the invention may also be prepared by the route shown in Scheme 6. 3-Methyl-1,2-benzenediamine is reacted with carbonyl diimidazole or phosgene to give 4-methylbenzimidazolone (XXXVI). This is refluxed with phosphorus oxychloride to give XXXVII which is protected and reacted with N-bromosuccinimine to give compound XXXIX. This is coupled with VIIb and the resulting adduct LX is hydrolyzed to LI. Reduction with lithium aluminum hydride alcohol LXII which was treated with carbon tetrabromide/triphenylphosphine to give compound 51. Compound 51 was refluxed in acetic acid to effect conversion to compound 6.