4,5-Diiodobenzene-1,2-diamine

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 50 mL round-bottom flask was charged with 2 (6.94 g, 19.3 mmol), and CuCN (6.91 g, 77.2 mmol, 4 eq), and a magnetic stirring bar. The vessel was capped with a septum and flushed with Ar for 10 min, and NMP (20 mL) was added. The vessel was heated to 120° C. for 3 h, then diluted with DMF (20 mL) and added to a hot aqueous solution of EDTA (88 g, 232 mmol, in 500 mL H2O) in a 1 L conical flask. Oxygen was bubbled through the mixture as it was stirred and heated for 2 h. After 2 h of this treatment, the dark heterogeneous mixture turned to a homogeneous green solution. The hot green solution was extracted twice with ethyl acetate, and the extracts were washed with water, followed by brine, dried over Na2SO4, filtered, and concentrated to dryness. The residue was recrystallized (EtOH/water), giving tiny tan needles (1.66 g, 55%): mp 262-264° C.; 1H NMR (d6-acetone) δ 5.40 (br s, 4H), 7.04 (s, 2H); 13C NMR (d6-acetone) δ 103.8, 117.1, 117.4, 139.4; FAB-MS obsd 158.0591, calcd 158.0592 (C6H6N4). The vessel was capped with a septum flushed with Ar for 10 min NMP (20 mL) was added diluted with DMF (20 mL) Oxygen was bubbled through the mixture as it heated for 2 h The hot green solution was extracted twice with ethyl acetate the extracts were washed with water dried over Na2SO4 filtered concentrated to dryness The residue was recrystallized (EtOH/water)

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

Procedure: Following a literature procedure, a sample of 1 (17.42 g, 41.5 mmol) and a magnetic stirring bar were added to a 500 mL conical flask fitted with a jacketed condenser. EtOH (95%, 150 mL) and conc. aqueous HCl (68.6 mL, 0.83 mol) were added, and the mixture was stirred and heated to boiling. Fe (18.59 g, 0.332 mol) was added in portions, resulting in foaming of the mixture and accelerated refluxing of the EtOH, which would subside within a few minutes of each addition. The reaction was heated for an additional 45 min beyond the final addition of Fe. A hot solution of EDTA (156 g, 0.411 mol, in 300 mL H2O) was added to the reaction mixture, and KOH pellets were added until the solution was alkaline to pH paper. The hot mixture was extracted twice with ethyl acetate and the extracts were combined, washed with water, followed by brine, dried over Na2SO4, filtered and concentrated to dryness. The residue was recrystallized (EtOH/water), giving tan needles (9.92 g, 66%): mp 135-136° C.; 1H NMR (d8-THF) δ 4.21 (brs, 4H), 7.03 (s, 2H); 13C NMR (d8-THF) δ 91.1, 124.5, 137.6; Anal. Calcd for C6H6I2N2: C, 20.02; H, 1.68; N, 7.78. Found: C, 20.19; H, 1.59, 7.71. fitted with a jacketed condenser heated to boiling resulting in foaming of the mixture would subside within a few minutes of each addition The reaction was heated for an additional 45 min beyond the final were added until the solution The hot mixture was extracted twice with ethyl acetate washed with water dried over Na2SO4 filtered concentrated to dryness The residue was recrystallized (EtOH/water)

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

Procedure: A solution was prepared from 0.9 g. of 4,5-diiodo-o-phenylenediamine and 25 ml. of ethanol. Five grams of diethyl ketomalonate were added and the resulting mixture was heated to refluxing temperature with stirring overnight. The reaction mixture was then cooled. Ethyl 6,7-diiodo-3,4-dihydro-3-oxo-2-quinoxaline carboxylate formed in the above reaction precipitated and was collected by filtration; yield=0.8 g.; mp=275°-276° C. A solution was prepared from 0.9 g the resulting mixture was heated to refluxing temperature The reaction mixture was then cooled

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 50 mL round-bottom flask was charged with 2 (6.94 g, 19.3 mmol), and CuCN (6.91 g, 77.2 mmol, 4 eq), and a magnetic stirring bar. The vessel was capped with a septum and flushed with Ar for 10 min, and NMP (20 mL) was added. The vessel was heated to 120° C. for 3 h, then diluted with DMF (20 mL) and added to a hot aqueous solution of EDTA (88 g, 232 mmol, in 500 mL H2O) in a 1 L conical flask. Oxygen was bubbled through the mixture as it was stirred and heated for 2 h. After 2 h of this treatment, the dark heterogeneous mixture turned to a homogeneous green solution. The hot green solution was extracted twice with ethyl acetate, and the extracts were washed with water, followed by brine, dried over Na2SO4, filtered, and concentrated to dryness. The residue was recrystallized (EtOH/water), giving tiny tan needles (1.66 g, 55%): mp 262-264° C.; 1H NMR (d6-acetone) δ 5.40 (br s, 4H), 7.04 (s, 2H); 13C NMR (d6-acetone) δ 103.8, 117.1, 117.4, 139.4; FAB-MS obsd 158.0591, calcd 158.0592 (C6H6N4). The vessel was capped with a septum flushed with Ar for 10 min NMP (20 mL) was added diluted with DMF (20 mL) Oxygen was bubbled through the mixture as it heated for 2 h The hot green solution was extracted twice with ethyl acetate the extracts were washed with water dried over Na2SO4 filtered concentrated to dryness The residue was recrystallized (EtOH/water)

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

Procedure: Following a literature procedure, a sample of 1 (17.42 g, 41.5 mmol) and a magnetic stirring bar were added to a 500 mL conical flask fitted with a jacketed condenser. EtOH (95%, 150 mL) and conc. aqueous HCl (68.6 mL, 0.83 mol) were added, and the mixture was stirred and heated to boiling. Fe (18.59 g, 0.332 mol) was added in portions, resulting in foaming of the mixture and accelerated refluxing of the EtOH, which would subside within a few minutes of each addition. The reaction was heated for an additional 45 min beyond the final addition of Fe. A hot solution of EDTA (156 g, 0.411 mol, in 300 mL H2O) was added to the reaction mixture, and KOH pellets were added until the solution was alkaline to pH paper. The hot mixture was extracted twice with ethyl acetate and the extracts were combined, washed with water, followed by brine, dried over Na2SO4, filtered and concentrated to dryness. The residue was recrystallized (EtOH/water), giving tan needles (9.92 g, 66%): mp 135-136° C.; 1H NMR (d8-THF) δ 4.21 (brs, 4H), 7.03 (s, 2H); 13C NMR (d8-THF) δ 91.1, 124.5, 137.6; Anal. Calcd for C6H6I2N2: C, 20.02; H, 1.68; N, 7.78. Found: C, 20.19; H, 1.59, 7.71. fitted with a jacketed condenser heated to boiling resulting in foaming of the mixture would subside within a few minutes of each addition The reaction was heated for an additional 45 min beyond the final were added until the solution The hot mixture was extracted twice with ethyl acetate washed with water dried over Na2SO4 filtered concentrated to dryness The residue was recrystallized (EtOH/water)

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

Procedure: Following a literature procedure, a sample of 1 (17.42 g, 41.5 mmol) and a magnetic stirring bar were added to a 500 mL conical flask fitted with a jacketed condenser. EtOH (95%, 150 mL) and conc. aqueous HCl (68.6 mL, 0.83 mol) were added, and the mixture was stirred and heated to boiling. Fe (18.59 g, 0.332 mol) was added in portions, resulting in foaming of the mixture and accelerated refluxing of the EtOH, which would subside within a few minutes of each addition. The reaction was heated for an additional 45 min beyond the final addition of Fe. A hot solution of EDTA (156 g, 0.411 mol, in 300 mL H2O) was added to the reaction mixture, and KOH pellets were added until the solution was alkaline to pH paper. The hot mixture was extracted twice with ethyl acetate and the extracts were combined, washed with water, followed by brine, dried over Na2SO4, filtered and concentrated to dryness. The residue was recrystallized (EtOH/water), giving tan needles (9.92 g, 66%): mp 135-136° C.; 1H NMR (d8-THF) δ 4.21 (brs, 4H), 7.03 (s, 2H); 13C NMR (d8-THF) δ 91.1, 124.5, 137.6; Anal. Calcd for C6H6I2N2: C, 20.02; H, 1.68; N, 7.78. Found: C, 20.19; H, 1.59, 7.71. fitted with a jacketed condenser heated to boiling resulting in foaming of the mixture would subside within a few minutes of each addition The reaction was heated for an additional 45 min beyond the final were added until the solution The hot mixture was extracted twice with ethyl acetate washed with water dried over Na2SO4 filtered concentrated to dryness The residue was recrystallized (EtOH/water)

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 50 mL round-bottom flask was charged with 2 (6.94 g, 19.3 mmol), and CuCN (6.91 g, 77.2 mmol, 4 eq), and a magnetic stirring bar. The vessel was capped with a septum and flushed with Ar for 10 min, and NMP (20 mL) was added. The vessel was heated to 120° C. for 3 h, then diluted with DMF (20 mL) and added to a hot aqueous solution of EDTA (88 g, 232 mmol, in 500 mL H2O) in a 1 L conical flask. Oxygen was bubbled through the mixture as it was stirred and heated for 2 h. After 2 h of this treatment, the dark heterogeneous mixture turned to a homogeneous green solution. The hot green solution was extracted twice with ethyl acetate, and the extracts were washed with water, followed by brine, dried over Na2SO4, filtered, and concentrated to dryness. The residue was recrystallized (EtOH/water), giving tiny tan needles (1.66 g, 55%): mp 262-264° C.; NMR (d6-acetone) δ 5.40 (br s, 4H), 7.04 (s, 2H); 13C NMR (d6-acetone) δ 103.8, 117.1, 117.4, 139.4; FAB-MS obsd 158.0591, calcd 158.0592 (C6H6N4). The vessel was capped with a septum flushed with Ar for 10 min NMP (20 mL) was added diluted with DMF (20 mL) Oxygen was bubbled through the mixture as it heated for 2 h The hot green solution was extracted twice with ethyl acetate the extracts were washed with water dried over Na2SO4 filtered concentrated to dryness The residue was recrystallized (EtOH/water)

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

Procedure: Following a literature procedure, a sample of 1 (17.42 g, 41.5 mmol) and a magnetic stirring bar were added to a 500 mL conical flask fitted with a jacketed condenser. EtOH (95%, 150 mL) and conc. aqueous HCl (68.6 mL, 0.83 mol) were added, and the mixture was stirred and heated to boiling. Fe (18.59 g, 0.332 mol) was added in portions, resulting in foaming of the mixture and accelerated refluxing of the EtOH, which would subside within a few minutes of each addition. The reaction was heated for an additional 45 min beyond the final addition of Fe. A hot solution of EDTA (156 g, 0.411 mol, in 300 mL H2O) was added to the reaction mixture, and KOH pellets were added until the solution was alkaline to pH paper. The hot mixture was extracted twice with ethyl acetate and the extracts were combined, washed with water, followed by brine, dried over Na2SO4, filtered and concentrated to dryness. The residue was recrystallized (EtOH/water), giving tan needles (9.92 g, 66%): mp 135-136° C.; 1H NMR (d8-THF) δ 4.21 (brs, 4H), 7.03 (s, 2H); 13C NMR (d8-THF) δ 91.1, 124.5, 137.6; Anal. Calcd for C6H6I2N2: C, 20.02; H, 1.68; N, 7.78. Found: C, 20.19; H, 1.59, 7.71. fitted with a jacketed condenser heated to boiling resulting in foaming of the mixture would subside within a few minutes of each addition The reaction was heated for an additional 45 min beyond the final were added until the solution The hot mixture was extracted twice with ethyl acetate washed with water dried over Na2SO4 filtered concentrated to dryness The residue was recrystallized (EtOH/water)

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

Procedure: A solution was prepared from 0.9 g. of 4,5-di-iodo-o-phenylenediamine and 25 ml. of ethanol. Five grams of diethyl ketomalonate were added and the resulting mixture was heated to refluxing temperature with stirring overnight. The reaction mixture was then cooled. Ethyl 6,7-di-iodo-3,4-dihydro-3-oxo-2-quinoxaline carboxylate formed in the above reaction precipitated and was collected by filtration; yield=0.8 g.; mp=275°-276° C. A solution was prepared from 0.9 g the resulting mixture was heated to refluxing temperature The reaction mixture was then cooled

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

Procedure: A solution was prepared from 0.9 g. of 4,5-diiodo-o-phenylenediamine and 25 ml. of ethanol. Five grams of diethyl ketomalonate were added and the resulting mixture was heated to refluxing temperature with stirring overnight. The reaction mixture was then cooled. Ethyl 6,7-diiodo-3,4-dihydro-3-oxo-2-quinoxaline carboxylate formed in the above reaction precipitated and was collected by filtration; yield=0.8 g.; mp=275°-276° C. A solution was prepared from 0.9 g the resulting mixture was heated to refluxing temperature The reaction mixture was then cooled

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 50 mL round-bottom flask was charged with 2 (6.94 g, 19.3 mmol), and CuCN (6.91 g, 77.2 mmol, 4 eq), and a magnetic stirring bar. The vessel was capped with a septum and flushed with Ar for 10 min, and NMP (20 mL) was added. The vessel was heated to 120° C. for 3 h, then diluted with DMF (20 mL) and added to a hot aqueous solution of EDTA (88 g, 232 mmol, in 500 mL H2O) in a 1 L conical flask. Oxygen was bubbled through the mixture as it was stirred and heated for 2 h. After 2 h of this treatment, the dark heterogeneous mixture turned to a homogeneous green solution. The hot green solution was extracted twice with ethyl acetate, and the extracts were washed with water, followed by brine, dried over Na2SO4, filtered, and concentrated to dryness. The residue was recrystallized (EtOH/water), giving tiny tan needles (1.66 g, 55%): mp 262-264° C.; 1H NMR (d6-acetone) δ 5.40 (br s, 4H), 7.04 (s, 2H); 13C NMR (d6-acetone) δ 103.8, 117.1, 117.4, 139.4; FAB-MS obsd 158.0591, calcd 158.0592 (C6H6N4). The vessel was capped with a septum flushed with Ar for 10 min NMP (20 mL) was added diluted with DMF (20 mL) Oxygen was bubbled through the mixture as it heated for 2 h The hot green solution was extracted twice with ethyl acetate the extracts were washed with water dried over Na2SO4 filtered concentrated to dryness The residue was recrystallized (EtOH/water)

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

Procedure: Following a literature procedure, a sample of 1 (17.42 g, 41.5 mmol) and a magnetic stirring bar were added to a 500 mL conical flask fitted with a jacketed condenser. EtOH (95%, 150 mL) and conc. aqueous HCl (68.6 mL, 0.83 mol) were added, and the mixture was stirred and heated to boiling. Fe (18.59 g, 0.332 mol) was added in portions, resulting in foaming of the mixture and accelerated refluxing of the EtOH, which would subside within a few minutes of each addition. The reaction was heated for an additional 45 min beyond the final addition of Fe. A hot solution of EDTA (156 g, 0.411 mol, in 300 mL H2O) was added to the reaction mixture, and KOH pellets were added until the solution was alkaline to pH paper. The hot mixture was extracted twice with ethyl acetate and the extracts were combined, washed with water, followed by brine, dried over Na2SO4, filtered and concentrated to dryness. The residue was recrystallized (EtOH/water), giving tan needles (9.92 g, 66%): mp 135-136° C.; 1H NMR (d8-THF) δ 4.21 (brs, 4H), 7.03 (s, 2H); 13C NMR (d8-THF) δ 91.1, 124.5, 137.6; Anal. Calcd for C6H6I2N2: C, 20.02; H, 1.68; N, 7.78. Found: C, 20.19; H, 1.59, 7.71. fitted with a jacketed condenser heated to boiling resulting in foaming of the mixture would subside within a few minutes of each addition The reaction was heated for an additional 45 min beyond the final were added until the solution The hot mixture was extracted twice with ethyl acetate washed with water dried over Na2SO4 filtered concentrated to dryness The residue was recrystallized (EtOH/water)