9,10-Bis(2-naphthyl)anthracene-2-ylboronic acid

Prepared according to procedure described inEP13 2-bromo-9, 1 0-di(naphthalen-2-yl)anthracene (10.00 g, 1.0 eq, 19.63 mmol) was dissolved in THF (140 mE) and cooled to —78° C. At this temperature n-BuEi (2.5M in hexane, 10.2 mE, 1.3 eq, 25.52 mmol) was added dropwise and the mixture was stirred for 2 hours. Afterwards, B(OMe)3 (6.12 g, 3.0 eq, 58.89 mmol) was added at -78° C. and the reaction mixture was allowed to warm up to room temperature. After stirring for 17 hours the mixture was quenched with HC1, the yellow precipitate was filtered off and washed with water (2x30 mE). The residue was dried in vacuo and used without further purification. Yield: 9.8 g (100percent)Synthesis of Intermediate 1c; 5 g of Intermediate 1b (9.81 mmol) was dissolved in 70 ml of THF dried under nitrogen atmosphere, and 4.7 ml of lithium butyl (11.8 mmol) was added to the mixture at -78° C. The mixture was stirred for one hour at the same temperature, and then 2.20 ml of trimethyl borate (29.4 mmol) was added to the mixture. The temperature of the mixture was increased to room temperature, and one hour later, 2N of an aqueous hydrochloric acid solution was added to the mixture and stirred for 3 hours. The obtained solid compound was filtered while being washed with toluene to obtain 3.27 g of light-yellow Intermediate 1c (yield 70percent).Synthesis of Intermediate 1c; 5 g of Intermediate 1b (9.81 mmol) was dissolved in 70 ml of THF dried under nitrogen atmosphere, and 4.7 ml of lithium butyl (11.8 mmol) was added to the mixture at -78°C. The mixture was stirred for one hour at the same temperature, and then 2.20ml of trimethyl borate (29.4 mmol) was added to the mixture. The temperature of the mixture was increased to room temperature, and one hour later, 2N of an aqueous hydrochloric acid solution was added to the mixture and stirred for 3 hours. The obtained solid compound was filtered while being washed with toluene to obtain 3.27 g of light-yellow Intermediate 1c (yield 70percent).Synthesis of Intermediate 1c; The intermediate 1b (5g, 9.81 mmol) was dissolved in 70 ml of dried THF under a nitrogen atmosphere, and butyl lithium (4.7ml, 11.8mmol) was added dropwise thereto at -78° C. The reaction mixture was stirred at -78° C for one hour, and trimethylborate (2.20ml, 29.4mmol) was added thereto. The reaction solution was heated to room temperature and incubated for one hour. Then, a 2N HCl solution was added thereto, and the resultant solution was stirred for three hours. The resultant solid compound was washed and filtered with toluene to yield intermediate 1c as a light yellow powder (3.27g, yield: 70percent).In an argon atmosphere, 100 mL of dehydrated THF were added to 10 g (20 mmol) of 2-bromo-9, 10-di(2-naphtyl) anthracene, and the temperature of the mixture was cooled to -78° C. Then, 14 mL of n-butyllithium (in hexane, 1.6 mol/L) were dropped. After the mixture had been stirred at -78° C for 1 hour, the temperature of the mixture was increased to 0°C. The temperature of the mixture was cooled to -78° C again, and 6.6 mL (60 mmol) of trimethoxyborane were added. The mixture was stirred at -78° C for 1 hour, and was then stirred at room temperature for 2 hours. 100 mL of 10-mass percent hydrochloric were added, and the whole was stirred for 1 hour, followed by filtration. The resultant solid was washed with toluene to obtain 4.7 g of 9, 10-diphenylanthracene-2-boronic acid (50percent yield).3-2) Synthesis of 2-bromo-9, 10-di(2-naphthyl)anthracene 190 g (0.37 mol) of 2-bromo-9, 10-di(2-naphthyl)anthracene obtained from 3-1) was dissolved with 1.5 L of THF in a 5L flask and the temperature was cooled to -78°C. Then, 279 ml (0.44 mol) of 1.6 M n-BuLi was slowly added dropwise thereto. After one hour, 140 g (0.74 mol) of B(OiPr)Under nitrogen of 2-bromo -9, 10- di (naphthalene-2-yl) anthracene ( 10g , 1.0eq ) in THF 150 ml The mixture was after n-BuLi (11.8 ml, 1.5eq) cooled to -78 to It was added slowly and stirred for 1 hour. After adding the trimethyl borate ( 3.2ml , 1.5eq ) to the reaction mixture after 2 hours cooled to 0 back extracted with MC it was added to 6M HCl . The concentrate EA: hexane = 1: 1 column separation to obtain a white solid compound 97-1 . ( 5.5g , 60 percent )