3,6-Dibromo-9,10-phenanthrenedione

A mixture of phenanthrenequinone (5.0 g, 24 mmol), Br2 (2.6 mL, 50.4 mmol), nitrobenzene (45 mL), and benzoyl peroxide (0.25 g, 1 mmol) was exposed to a tungsten lamp and heated at 60 °C for 17 h. The reaction mixture was allowed to cool down to room temperature. The light brown crystals were collected by filtration and washed with ethanol. A second of the crop of crystals were obtained after cooling in ice. The crystals were dried under vacuum at 60 °C overnight to give light brown crystals (7.84 g, 90percent). The product was recrystallized from nitrobenzene to give orange brown crystals. 20.50 g of phenanthrenequinone, 48 g of bromine, 1.0 g of benzoyl peroxide and 300 ml of nitrobenzene, Add reflux for 2-3 hours, Cool down to room temperature, filter, The solid was washed with 400 ml of ethanol and dried to give 29.21 g of TM-1.The yield was 82percent.In a 250 mL three-necked flask, Followed by adding 5.2 g of phenanthrenequinone, 0.4 g of benzoyl peroxide, Liquid bromine 1.5g and solvent nitrobenzene 160mL, raised to 140 , the reaction to the hydrogen bromide gas generated after the continued drop of liquid bromine 16g. After 8 h, the reaction was cooled toThe filter cake was washed with absolute ethanol and several times until the filtrate was colorless and 7.32 g (80percent) of the desired solid product was obtained.9, 10-phenanthrenequinone (10.006 g, 48.02 mmol) was dissolved 60 mL of nitrobenzene, Under nitrogen protection, Add benzoyl peroxide (0.980 g, 4.05 mmol), Add 1mLBr2, Heated to 120 ° C, Produce a large amount of HBr gas, And then slowly dropping 4 mL of Br2, After the dropwise addition, the mixture was stirred at 120 ° C for 1.5 h, Cooled to room temperature, Adding a small amount of saturated NaHSO3 solution, Then add 60mL petroleum ether, a large number of yellow solid appears, filter, Wash the filter cake with a large amount of petroleum ether, A yellow solid (11.20 g, 80percent) was obtained.EXAMPLE 5 Under nitrogen protection, To 230 ml of nitrobenzene were successively added 42.2 g (0.203 mol)Of 4a, 10a-dihydro-9, 10-phenanthrenequinone and 300 mg (0.002 mol) of aluminum chloride, After stirring and heating to 105 ° C, 84.2 g (0.527 mol) of liquid bromine was added over 40 minutes and reacted for 3 hours.After cooling to room temperature, the crude product was filtered off and recrystallized from xylene to give 46.9 g (0.128 mol) of Intermediate A in a 63percent yield.Preparation of Compound B; [98] Compound A (20 g, 96.05 mmol), benzoyl peroxide (3.1 g, 9.60 mmol, 75percent), nitrobenzene (300 mL) and BrGeneral procedure: The oxidation was carried out using 0.4g of chromium trioxide (4mmol), which was added to a solution of 0.2g of the phenanthrene 9a–d (1.12mmol; 1equiv) in 20mL of glacial acetic acid. The resulting mixture was warmed gently until no material remained undissolved and then the solution was heated at reflux for 1h, cooled to room temperature, and then poured into water. The mixture was filtered, washed with water, and then crystallized from hexane.

Molecular Weight:366.00
XLogP3:3.9
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