2,6-Dibromoanthraquinone

Yellow crystalline powder

Synthesis Synthesis of Compound 8 2-1) Synthesis of 2, 6-dibromoanthraquinone 198.2 g (1.5 mol) of tert-butylnitrite and 279.1 g (1.2 mol) of Cu(II)Br were diluted with 6000 ml of acetonitirle in a 10L flask, and then the temperature was increased to 65°C and 119.1 g (0.5 mol) of 2, 6-diaminoanthraquinone was slowly added thereto for 5 minutes. When formation of NTo a three-necked flask containing a mixture of 2, 6-diaminoanthracene-9, 10-dione (5g, 21.0mmol), CuBrA three-necked round-bottomed flask (500 mL) was charged with CuBr2 (28.0 g, 125 mmol), acetonitrile (200 mL) and t-BuONO (17.2 mL, 150 mmol). The resulting dark green-brown solution was heated to 70 °C and 2, 6-diaminoanthraquinone (11.6 g, 49 mmol) was added portionwise over 10 min. The stirring was continued at 70 °C for 4 h. The reaction mixture was allowed to cool to rt and then poured on 6M HCl (400 mL). The formed precipitate was filtered off trough a sinter funnel (por. 3), washed with water and a small amount of ethanol and then dried on air. The reaction gave the pure product 30 (17.2 g, 97percent) in the form of yellow solid.62.6 g (255 mmol) of 2, 6-diaminoanthraquinone and 124 g (550 mmol) of CuBr1) This example illustrates the synthesis of an exemplary compound (Compound 7). It will be apparent to one skilled in the art that other compounds represented by Formulas 1 or 2 can be synthesized in a manner similar to that described in A 500 imL 3-neck round-bottomed flask was charged with anhydrous copper bromide (CuBrT-BuONO (1.95 g, 18.88 mmol), CHSolution made by dissolving 3.44 g of 2, 6-diaminoanthraquinone (14 mmol) in 50 ml of anhydrousacetonitrile was dropped to the mixture of 7.76 g of CuBr2(35 mmol) and 5.16 ml of t-BuNO2 at 65 C. 200 ml ofHCl was added after the reaction. The solution was washedsufficiently and filtered using ethanol and water. The precipitatewas dissolved in chloroform and re-filtered afteradding MgSO4. The solvent was removed by evaporationand the product was re-precipitated with chloroform andMeOH to obtain 3.1 g of brown solid (yield: 58percent).1H-NMR (300 MHz, CDCl3, ): 8.43 (s, 2H), 8.17(d, 2H), 7.95 (d, 2H).Procedure: 2, 6-diaminoanthraquinone (compound S7, 2.35 g, 10 mmol, 1 eq.) andcopper(II)bromide (5.02 g, 22.5 mmol, 2.25 eq.) were added to an oven-dried round-bottomedflask. Acetonitrile (50 ml) was added forming a black suspension. Tert-butyl nitrite (90percent, 2.94 ml, 22.5 mmol, 2.25 eq.) was then added slowly via syringe while the reaction mixture stirred at roomtemperature. The reaction mixture was then heated at 65 °C for 2.5 hours, after which time it wascooled to room temperature and 3M HCl (25 ml) was added, followed by distilled water (25 ml).The reaction stirred for 20 minutes and then was vacuum filtered giving a brown solid. The brownsolid was washed twice with distilled water and once with ethanol, before being recrystallized inchloroform, giving a tan solid in 43percent yield (1.43 g).Preparation of Compound (6) [2 , 6-dibromoanthraquinone] In acetonitrile (150 ml) , dissolved were t-butylnitrite (30.3 g, 0.294 mol) and CuBrAminoanthraquinone is used10g, t-Bu ONO 10g, CuBr2 22g, and CH3CN 170ml was added to a 500ml round bottom flask, Magnetic stirring and nitrogen protection, stirring and heating to 65 ° C for 2 hours, Next, 100 ml of 35percent hydrochloric acid (HCl) solution was added to the flask.The resulting product was filtered and washed with CH 3 CN and the resulting product was recrystallized, The method is to use 500ml 1, 4-dioxane (1, 4-dioxane) 500ml a round bottom flask, Magnetically stirred and protected with nitrogen, Heated to 115 ° C for 40 minutes, The solution was filtered again and 10.46 g of product was obtained as a khaki-colored powdery product.The yield of this step is 35.8percentSynthesis of Intermediate 1 2.38 g (10mmol) of 2, 6-diaminoanthraquinone was dispersed in a 48 weight percent HBr aqueous solution, and then 1.41 g (20.4 mmol) of NaNO23.8 g (100 mmol) of 2, 6-diaminoanthraquinone were dispersed into a 48-mass percent aqueous solution of hydrogen bromide, and then 14.1 g (204 mmol) of sodium nitrite were added. After the generation of a gas had been completely stopped, 63 mL of an aqueous solution of 30 g (206 mmol) of copper bromide/48-mass percent hydrogen bromide were dropped together with 50 mL of ethanol. The reaction solution was gradually heated, and was refluxed under heating. The reaction solution was stood to cool to room temperature, and water was added. The precipitated solid was filtered out and washed with water. The resultant solid was purified by means of silica gel column chromatography to obtain 10.0 g of 2, 6-dibromoanthraquinone (27percent yield) .Synthesis of Compound 1012, 6-Diaminoanthraquinone (23.8 g, 100 mmol) was dispersed in 48 wt percent of a hydrogen bromide aqueous solution. Sodium nitrite (NaNOSynthesis of Compound 101 2, 6-Diaminoanthraquinone (23.8 g, 100 mmol) was dispersed in 48 wtpercent of a hydrogen bromide aqueous solution. Sodium nitrite (NaNO2, 14.1 g, 204 mmol) was slowly added to the mixture at-20°C, which evolved nitrogen gas. After gas evolution was completed, a solution of copper bromide (CuBr, 29.5 g, 206 mmol) dissolved in 48 wtpercent of a hydrogen bromide aqueous solution (63 mL) was slowly added to the mixture together with a small amount of ethanol (50 mL). The temperature of the resulting mixture was slowly elevated and then the mixture was slowly refluxed. The result was cooled to room temperature and was dilute with water. Precipitate in the mixture was filtered off with suction, washed with water, and dried in vacuo. Then, the dried precipitate was dissolved in chloroform, filtered through a short column of silica gel, and concentrated under reduced pressure. Purification by column chromatography and recrystallization from chloroform yielded Compound 101 (10.0 g, 27percent). The analysis result of the compound is: 1H NMR (300 MHz, CDCl3), 8.44 (d, J = 2.1 Hz, 2H), 8.18 (d, J = 8.0 Hz, 2H), 7.95 (dd, J = 2.1, 8.0 Hz, 2H.)[Preparative Example 1] Preparation of Compound A[58] 2, 6-Diaminoanthraquinone (23.8 g, 100 mmol) was dispersed in 48 wtpercent of a hydrogen bromide aqueous solution. Sodium nitrite (NaNO , 14.1 g, 204 mmol) was slowly added to the mixture at -20°C, which evolved nitrogen gas. After gas evolution was completed, a solution of copper bromide (CuBr, 29.5 g, 206 mmol) dissolved in 48 wtpercent of a hydrogen bromide aqueous solution (63 mL) was slowly added to the mixture together with a small amount of ethanol (50 mL). The temperature of the resulting mixture was slowly elevated and then the mixture was slowly refluxed. The mixture was cooled to room temperature and was diluted with water. The precipitate in the mixture was filtered off with suction, washed with water, and dried in vacuo. The dried precipitate was dissolved in chloroform, filtered through silica gel, and con- (Preparation of starting material represented by Chemical Formula a) [0040] 2, 6-Diaminoanthraquinone (23.8 g, 100 mmol) was dispersed in 48 wtpercent of a hydrogen bromide aqueous solution, and then sodium nitrite (NaNOIn a 250 mL round bottom flask, 0.7 g of

Molecular Weight:366.00
XLogP3:4.2
Hydrogen Bond Acceptor Count:2
Exact Mass:365.87141
Monoisotopic Mass:363.87345
Topological Polar Surface Area:34.1
Heavy Atom Count:18
Complexity:346
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes