4,6-diaminobenzene-1,3-diol;dihydrochloride

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

Procedure: After the active carbon treatment, solids are deposited by salting out with addition of concentrated hydrochloric acid, and an amount of added hydrochloric acid may be 4-20 times by mole of 4,6-diaminoresorcinol. It is influenced by the amount of water from the economical viewpoint, but 4-8 times by mole are preferable. 4,6-Diaminoresorcinol dihydrochloride is obtained by drying after filtration.

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

Procedure: 30 g of crude 4,6-dinitroresorcin were recrystallized in 1,500 g of ethanol to obtain 24.1 g of purified 4,6-dinitroresorcin. Next, 4.0 g of this purified 4,6-dinitroresorcin were added to methanol, and 0.0396 g of 5% palladium carbon (a 50% wet product) was then added thereto, followed by hydrogenation at 60° C. under an average hydrogen pressure of 0.8 MPaG. The reaction mass was poured into a 5% aqueous hydrochloric acid solution containing 6,000 ppm of stannous chloride, and then filtered to remove the catalyst. Afterward, analysis was carried out by HPLC, and it was confirmed that desired 4,6-diaminoresorcin was produced in a yield of 96.2 mol %. The solvent was removed from the filtrate by an evaporator to obtain the crystals of crude 4,6-dinitroresorcin. The crystals were dissolved in 21.3 g of water containing 0.32 g of stannous chloride, and 0.2 g of activated carbon was added to the solution. Thereafter, the solution was stirred for 30 minutes and then filtered to remove the activated carbon. When 16.0 g of 36% hydrochloric acid were gradually added dropwise to the filtrate, the gradual deposition of crystals was observed. The crystals were collected by filtration and then dried at 50° C. under reduced pressure to obtain 3.03 g (yield=46.4%) of 4,6-diaminoresorcin dihydrochloride. was then added followed by hydrogenation at 60° C. under an average hydrogen filtered to remove the catalyst was produced in a yield of 96.2 mol % The solvent was removed from the filtrate by an evaporator to obtain the crystals of crude 4,6-dinitroresorcin was added to the solution filtered to remove the activated carbon When 16.0 g of 36% hydrochloric acid were gradually added dropwise to the filtrate The crystals were collected by filtration dried at 50° C. under reduced pressure

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

Procedure: 30 g of crude 4,6-dinitroresorcin were recrystallized in 1,500 g of ethanol to obtain 24.1 g of purified 4,6-dinitroresorcin. Next, 4.0 g of this purified 4,6-dinitroresorcin were added to methanol, and 0.0396 g of 5% palladium carbon (a 50% wet product) was then added thereto, followed by hydrogenation at 60° C. under an average hydrogen pressure of 0.8 MPaG. The reaction mass was poured into a 5% aqueous hydrochloric acid solution containing 6,000 ppm of stannous chloride, and then filtered to remove the catalyst. Afterward, analysis was carried out by HPLC, and it was confirmed that desired 4,6-diaminoresorcin was produced in a yield of 96.2 mol %. The solvent was removed from the filtrate by an evaporator to obtain the crystals of crude 4,6-dinitroresorcin. The crystals were dissolved in 21.3 g of water containing 0.32 g of stannous chloride, and 0.2 g of activated carbon was added to the solution. Thereafter, the solution was stirred for 30 minutes and then filtered to remove the activated carbon. When 16.0 g of 36% hydrochloric acid were gradually added dropwise to the filtrate, the gradual deposition of crystals was observed. The crystals were collected by filtration and then dried at 50° C. under reduced pressure to obtain 3.03 g (yield=46.4%) of 4,6-diaminoresorcin dihydrochloride. was then added followed by hydrogenation at 60° C. under an average hydrogen filtered to remove the catalyst was produced in a yield of 96.2 mol % The solvent was removed from the filtrate by an evaporator to obtain the crystals of crude 4,6-dinitroresorcin was added to the solution filtered to remove the activated carbon When 16.0 g of 36% hydrochloric acid were gradually added dropwise to the filtrate The crystals were collected by filtration dried at 50° C. under reduced pressure

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

Procedure: A one-liter Hastelloy C autoclave equipped with a gas dispersion stirrer and cooling coil is charged with 100.0 g (0.5 mole) of the 4,6-dinitro-1,3-benzenediol, 500 ml of n-propanol, ~7.0 g of 10 percent Pd/C and 10.0 ml of H2O. The sealed reactor is charged with 50 psi of H2 and the temperature is brought to 40° C. and maintained between 40° C.-50° C. during the course of the reaction. After a brief induction period, the uptake of hydrogen becomes extremely rapid and H2 pressure is maintained at about atmospheric pressure during the reaction. Upon completion, no further uptake of H2 is observed. The reactor is cooled to room temperature, opened and 300 ml of concentrated HCl containing ~10 g of SnCl2.2H2O is added to the reaction mixture. The crude product with the catalyst is isolated by filtration. This material is dissolved in 200 g of H2O at 85° C. and the catalyst is removed by filtration. H2O (100-300 ml) is added to the filtrate along with 500 ml of HCl and the catalyst-free material is precipitated from the brown solution. Recrystallization may be carried out in the existing solvent or the semi-pure material can be isolated and air dried to afford 100 g of crude diamino resorcinol dihydrochloride (predominantly 4,6-diamino-1,3-benzenediol dihydrochloride in 95.0 mole percent yield based on the 4,6-dinitro-1,3benzenediol. cooling coil The sealed reactor is charged with 50 psi of H2 is brought to 40° C. maintained between 40° C.-50° C. during the course of the reaction H2 pressure is maintained at about atmospheric pressure during the reaction The crude product with the catalyst is isolated by filtration the catalyst is removed by filtration H2O (100-300 ml) is added to the filtrate along with 500 ml of HCl the catalyst-free material is precipitated from the brown solution Recrystallization the semi-pure material can be isolated air dried

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

Procedure: 30 g of crude 4,6-dinitroresorcin were recrystallized in 1,500 g of ethanol to obtain 24.1 g of purified 4,6-dinitroresorcin. Next, 4.0 g of this purified 4,6-dinitroresorcin were added to methanol, and 0.0396 g of 5% palladium carbon (a 50% wet product) was then added thereto, followed by hydrogenation at 60° C. under an average hydrogen pressure of 0.8 MPaG. The reaction mass was poured into a 5% aqueous hydrochloric acid solution containing 6,000 ppm of stannous chloride, and then filtered to remove the catalyst. Afterward, analysis was carried out by HPLC, and it was confirmed that desired 4,6-diaminoresorcin was produced in a yield of 96.2 mol %. The solvent was removed from the filtrate by an evaporator to obtain the crystals of crude 4,6-dinitroresorcin. The crystals were dissolved in 21.3 g of water containing 0.32 g of stannous chloride, and 0.2 g of activated carbon was added to the solution. Thereafter, the solution was stirred for 30 minutes and then filtered to remove the activated carbon. When 16.0 g of 36% hydrochloric acid were gradually added dropwise to the filtrate, the gradual deposition of crystals was observed. The crystals were collected by filtration and then dried at 50° C. under reduced pressure to obtain 3.03 g (yield=46.4%) of 4,6-diaminoresorcin dihydrochloride. was then added followed by hydrogenation at 60° C. under an average hydrogen filtered to remove the catalyst was produced in a yield of 96.2 mol % The solvent was removed from the filtrate by an evaporator to obtain the crystals of crude 4,6-dinitroresorcin was added to the solution filtered to remove the activated carbon When 16.0 g of 36% hydrochloric acid were gradually added dropwise to the filtrate The crystals were collected by filtration dried at 50° C. under reduced pressure

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

Procedure: 30 g of crude 4,6-dinitroresorcin were recrystallized in 1,500 g of ethanol to obtain 24.1 g of purified 4,6-dinitroresorcin. Next, 4.0 g of this purified 4,6-dinitroresorcin were added to methanol, and 0.0396 g of 5% palladium carbon (a 50% wet product) was then added thereto, followed by hydrogenation at 60° C. under an average hydrogen pressure of 0.8 MPaG. The reaction mass was poured into a 5% aqueous hydrochloric acid solution containing 6,000 ppm of stannous chloride, and then filtered to remove the catalyst. Afterward, analysis was carried out by HPLC, and it was confirmed that desired 4,6-diaminoresorcin was produced in a yield of 96.2 mol %. The solvent was removed from the filtrate by an evaporator to obtain the crystals of crude 4,6-dinitroresorcin. The crystals were dissolved in 21.3 g of water containing 0.32 g of stannous chloride, and 0.2 g of activated carbon was added to the solution. Thereafter, the solution was stirred for 30 minutes and then filtered to remove the activated carbon. When 16.0 g of 36% hydrochloric acid were gradually added dropwise to the filtrate, the gradual deposition of crystals was observed. The crystals were collected by filtration and then dried at 50° C. under reduced pressure to obtain 3.03 g (yield=46.4%) of 4,6-diaminoresorcin dihydrochloride. was then added followed by hydrogenation at 60° C. under an average hydrogen filtered to remove the catalyst was produced in a yield of 96.2 mol % The solvent was removed from the filtrate by an evaporator to obtain the crystals of crude 4,6-dinitroresorcin was added to the solution filtered to remove the activated carbon When 16.0 g of 36% hydrochloric acid were gradually added dropwise to the filtrate The crystals were collected by filtration dried at 50° C. under reduced pressure

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

Procedure: 30 g of crude 4,6-dinitroresorcin were recrystallized in 1,500 g of ethanol to obtain 24.1 g of purified 4,6-dinitroresorcin. Next, 4.0 g of this purified 4,6-dinitroresorcin were added to methanol, and 0.0396 g of 5% palladium carbon (a 50% wet product) was then added thereto, followed by hydrogenation at 60° C. under an average hydrogen pressure of 0.8 MPaG. The reaction mass was poured into a 5% aqueous hydrochloric acid solution containing 6,000 ppm of stannous chloride, and then filtered to remove the catalyst. Afterward, analysis was carried out by HPLC, and it was confirmed that desired 4,6-diaminoresorcin was produced in a yield of 96.2 mol %. The solvent was removed from the filtrate by an evaporator to obtain the crystals of crude 4,6-dinitroresorcin. The crystals were dissolved in 21.3 g of water containing 0.32 g of stannous chloride, and 0.2 g of activated carbon was added to the solution. Thereafter, the solution was stirred for 30 minutes and then filtered to remove the activated carbon. When 16.0 g of 36% hydrochloric acid were gradually added dropwise to the filtrate, the gradual deposition of crystals was observed. The crystals were collected by filtration and then dried at 50° C. under reduced pressure to obtain 3.03 g (yield=46.4%) of 4,6-diaminoresorcin dihydrochloride. was then added followed by hydrogenation at 60° C. under an average hydrogen filtered to remove the catalyst was produced in a yield of 96.2 mol % The solvent was removed from the filtrate by an evaporator to obtain the crystals of crude 4,6-dinitroresorcin was added to the solution filtered to remove the activated carbon When 16.0 g of 36% hydrochloric acid were gradually added dropwise to the filtrate The crystals were collected by filtration dried at 50° C. under reduced pressure

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 mL, 3-necked, round-bottomed flask is charged with 150 mL of water, 21.4 g (0.1 mole) of 5-methoxy-2,4-dinitrophenol and 1.0 g of 10% palladium on carbon catalyst. The reaction is stirred under a nitrogen atmosphere for 3 to 4 minutes. The stirred reaction mixture is heated to 55° C. and hydrogen gas is sparged below the surface of the reaction mixture. After 10 minutes, 19.8 g (0.2 mole) of concentrated HCl is added through the condenser while hydrogenation is continued for 4 hours. The catalyst is removed by filtration and the filtrate is passed into a solution consisting of 0.5 g of stannous chloride dihydrate and 25 mL of concentrated HCl. This solution is then saturated with dry HCl gas and charged to a 600 mL 5 Hastalloy B autoclave. The reactor is heated to 150° C. for 18 hours and cooled to 25° C. The resulting product is isolated by filtration and dried under nitrogen to yield 19.7 g (90% yield) of crude 4,6-diaminoresorcinol dihydrochloride. The stirred reaction mixture hydrogen gas is sparged below the surface of the reaction mixture After 10 minutes is continued for 4 hours The catalyst is removed by filtration saturated with dry HCl gas and charged to a 600 mL 5 Hastalloy B autoclave The reactor is heated to 150° C. for 18 hours cooled to 25° C The resulting product is isolated by filtration dried under nitrogen

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2.5 g of 5-methoxy-2,4-diaminophenol and 25 mL of concentrated HCl is placed in a 45 mL Hastalloy C autoclave. The mixture is then heated to 140° C. for 16 hours at a pressure of about 200 psi. The reaction mixture is then cooled to 25° C., the reactor is vented and the product, a white solid, is filtered and dried to yield 1.2 g of crude 4,6-diaminoresorcinol dihydrochloride. The reaction mixture is then cooled to 25° C. the product, a white solid, is filtered dried

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

Procedure: A one-liter Hastalloy C autoclave equipped with a gas dispersion stirrer and cooling coil is charged with 117.3 g (0.5 mole) of 1,3-dihydroxy-2-chloro-4,6-dinitrobenzene, 400 ml of glacial acetic acid, 41 g (~0.5 mole) of NaOAc, ~7.0 g of 10 percent Pd/C and 100 ml of H2O. The sealed reactor is charged with 400 psi of H2 and the temperature is brought to 40° C. and maintained between 40°C.-50° C. during the course of the reaction. After a brief induction period, the uptake of hydrogen becomes extremely rapid and H2 pressure is maintained between 100-400 psi during the reaction. Upon completion, no further uptake of H2 is observed. The reactor is cooled to room temperature, opened and 400 ml of concentrated HCl containing ~10 g of SnC12.2H2O is added to the reaction mixture. The crude product with the catalyst is isolated by filtration. This material is dissolved in 200 g of H2O at 85° C. and the catalyst is removed by filtration. H2O (100-300 ml) is added to the filtrate along with 500 ml of HCl and the catalyst-free material is precipitated from the brown solution. Recrystallization may be carried out in the existing solvent or the semi-pure material can be isolated and air dried to afford 100 g of crude diamino resorcinol dihydrochloride, 4,6-diamino-1,3-benzenediol dihydrochloride (96.8 mole percent yield based on the 1,3-dihydroxy-2-chloro-4,6-dinitrobenzene). A one-liter Hastalloy C autoclave equipped with a gas dispersion stirrer cooling coil The sealed reactor is charged with 400 psi of H2 is brought to 40° C. maintained between 40°C.-50° C. during the course of the reaction H2 pressure is maintained between 100-400 psi during the reaction The crude product with the catalyst is isolated by filtration the catalyst is removed by filtration H2O (100-300 ml) is added to the filtrate along with 500 ml of HCl the catalyst-free material is precipitated from the brown solution Recrystallization the semi-pure material can be isolated air dried

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 mL, 3-necked, round-bottomed flask is charged with 150 mL of water, 21.4 g (0.1 mole) of 5-methoxy-2,4-dinitrophenol and 1.0 g of 10% palladium on carbon catalyst. The reaction is stirred under a nitrogen atmosphere for 3 to 4 minutes. The stirred reaction mixture is heated to 55° C. and hydrogen gas is sparged below the surface of the reaction mixture. After 10 minutes, 19.8 g (0.2 mole) of concentrated HCl is added through the condenser while hydrogenation is continued for 4 hours. The catalyst is removed by filtration and the filtrate is passed into a solution consisting of 0.5 g of stannous chloride dihydrate and 25 mL of concentrated HCl. This solution is then saturated with dry HCl gas and charged to a 600 mL 5 Hastalloy B autoclave. The reactor is heated to 150° C. for 18 hours and cooled to 25° C. The resulting product is isolated by filtration and dried under nitrogen to yield 19.7 g (90% yield) of crude 4,6-diaminoresorcinol dihydrochloride. The stirred reaction mixture hydrogen gas is sparged below the surface of the reaction mixture After 10 minutes is continued for 4 hours The catalyst is removed by filtration saturated with dry HCl gas and charged to a 600 mL 5 Hastalloy B autoclave The reactor is heated to 150° C. for 18 hours cooled to 25° C The resulting product is isolated by filtration dried under nitrogen

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2.5 g of 5-methoxy-2,4-diaminophenol and 25 mL of concentrated HCl is placed in a 45 mL Hastalloy C autoclave. The mixture is then heated to 140° C. for 16 hours at a pressure of about 200 psi. The reaction mixture is then cooled to 25° C., the reactor is vented and the product, a white solid, is filtered and dried to yield 1.2 g of crude 4,6-diaminoresorcinol dihydrochloride. The reaction mixture is then cooled to 25° C. the product, a white solid, is filtered dried