4-Dibenzothiopheneboronic acid

A is dissolved in anhydrous THF, cool down the temperature of the reaction was -78°C, n-BuLi (2.5 M inhexane) and then added dropwise slowly, and I, and the reaction was stirred for 1 hour at 0°C . Thereafter, the lower the temperature of the reaction to -78°C , and after dropwise addition of trimethyl borate, and stirred at room temperature for 12 hours. When the reaction terminated, the reaction mixture was introduced into a 2N-HCl aqueous solution, stirred for 30 minutes, and extracted with ether. After removing the reaction water in anhydrous MgSO4 and filtered under reduced pressure, to obtain the desired intermediate B The product resulting concentrated the organic solvent separated by column chromatography (yield: 82percent)Dibenzothiophene was dissolved in anhydrous tetrahydrofurane (THF), and the temperature of the reactants was lowered to −78° C. n-BuLi (2.5 M in hexane) was slowly added dropwise to the reactants, and then the reactants were stirred for 1 hour at 0° C. Subsequently, the temperature of the reactants was lowered to −78° C., and a triisopropyl borate solution dissolved in tetrahydrofuran (THF) was added dropwise to the reactants, followed by stirring for 12 hours at room temperature. Upon completion of the reaction, the reaction product was added with 1N-HCl aqueous solution, stirred for 30 minutes, and then extracted with ether. A small amount of water was removed from the extract by anhydrous magnesium sulfate (MgSODissolve dibenzo thiophene (Dibenzothiophene) in anhydrous tetrahydrofuran (tetrahydrofuran) (THF), it lowered the temperature of the reaction to -78°C . After dropwise addition of n-BuLi and (2.5 M in hexane) slowly, and the reaction was stirred for 1 hour at 0°C . Thereafter, the lower the temperature of the reaction to -78 °C, it was added dropwise a triisopropyl borate(triisopropyl borate) solution dissolved in tetrahydrofuran (tetrahydrofuran) (THF) and stirred at room temperature for 12 hours. After the reaction was completed after 1N- into an aqueous hydrochloric acid solution was stirred for 30 minutes, and extracted with ether. The small amount of water to the anhydrous magnesium sulfate (MgSO4), and separating the product produced by concentrating the filtered under reduced pressure after the organic solvent by using a column chromatography to obtain the desired intermediate A in a yield of 71percent.Dibenzothiophene was dissolved in tetrahydrofuran, and the temperature of the reaction product was lowered to −78° C. n-BuLi (2.5 M in hexane) was slowly added thereto, and the mixture was stirred for 1 hour at 0° C. Then, the temperature of the product was lowered to −78, and a triisopropyl borate solution dissolved in tetrahydrofuran was dropped thereto, followed by stirring for 12 hours at room temperature. After the completion of the reaction, the resultant product was added with 1N—HCl aqueous solution, stirred for 30 minutes, and extracted with ether. From the extract, a small amount of water was removed by magnesium sulfate anhydrous, followed by vacuum-filtration. Then, the product obtained after concentration of an organic solvent was purified by column chromatography to give a required intermediate A (yield: 71percent).Sub 6-1-1 (5.4g, 20mmol) were melted in the anhydrous Ether and the temperature of the reactant was lowered to -78°C and after n-BuLi (2.5M in hexane) (1.4g, 22mmol) were dipped as the slowly the reactant was mixed for 30 minutes. Thereafter, the temperature of the reactant was again lowered to -78 °C and Triisopropyl borates (5.6g, 30mmol) were dipped. At a room temperature, after it is stirred water is put in and it attenuates and 2N HCl is put. When reaction is completed, the organic compound which was dry to the MgSO4 and was the organic layer generated after doing the concentration was recrystallized as the ethyl acetate and water after doing the extraction with the silicagel column and the Sub 6-1 was obtained with 3.3 g (yield : 73percent).Sub 3-1 (5.3g, 20mmol) dissolved in anhydrous ether, Lowering the temperature of the reaction to -78°C, n-BuLi (2.5M in hexane) (1.4g, 22mmol) added dropwise slowly, and the reaction was stirred for 30 minutes. After lowering the temperature of the reaction back to -78°C and dropwise added triisopropyl borate (5.6g, 30mmol). After stirring atroom temperature, diluted with water and it binds the 2N HCl. After completion of reaction, ethyl acetate and water, the organic layerwas dried over MgSO4, concentrated and extracted the organics silicagelcolumn and recrystallized Sub 3-2 3.2g (yield: 71percent) was obtained and then produced.In nitrogen, clean and dry 1000ml three-necked bottle, Proportionately added 10a, Triisopropyl borate, THF, cool down to -80°C, Lithium butyl lithium was added dropwise, and the insulation was kept for 2 hours.Hydrochloric acid, washing, dehydration solvent, toluene beating, to 10b;HPLC: 99.5percent, yield: 60percent;Then slowly added dropwise to butyl lithium 477mL (1.194mol) stirreddibenzothiophene 200g (1.085mol) in a flask in anitrogen atmosphere in anhydrous tetrahydrofuran at 78° C 2L, and 2.5 mol. The temperature was raised to roomtemperature and stirred for 4 hours. It cooled back to 78° C and then added dropwise trimethylborate 363mL (3.255mol)slowly. It is gradually raised separating layer and the reaction solution was poured into 2L 1N aqueous hydrochloric acidsolution for 10 hours to room temperature. The organic layer is separated, washed with saturated brine 2L. After the organiclayer was separated and filtered, then dried over anhydrous magnesium sulfate. The filtrate was concentrated under reducedpressure and washed with acetone intermediate compound as a white solid [11]were prepared 150g (61percent).Under a nitrogen atmosphere, 300 g of anhydrous tetrahydrofuran was added to the reaction flask, stirring was continued, 22 g of dibenzothiophene was added and cooled to -30C.N-BuLi was slowly added dropwise to 70 mL of 2.0 M, and after stirring for 30 minutes, a solution of 1, 4, 7, 10-tetramethyl-1, 4, 7, 10-tetraazacyclododecane was slowly added dropwise.After incubation for 2 hours, 26 mL of trimethyl borate was slowly added dropwise at -30 ° C, stirred for 1 hr, slowly rose to room temperature and stirred for 1 hour.And 400 g of concentrated hydrochloric acid was added thereto, followed by stirring for 1 hour to carry out a hydrolysis reaction.The layers were allowed to stand, and the organic layer was washed three times with water (3 x 100 g).The aqueous layers were combined and the aqueous layer was extracted once with 100 ml of petroleum ether. The combined organic layers were dried over 50 g of anhydrous sodium sulfate and filtered.The filtrate was concentrated to dryness.With 100ml petroleum ether beating, suction filtration, drying, the product dibenzothiophene-4-boric acid 20g.In a 1-L reactor, tetrahydrofuran (500 mL) and dibenzothiophene (50 g, 271 mmol) were placed and cooled to −78° C. under a nitrogen atmosphere. After 30 min, drops of 1.6 M n-butyllithium (203 mL, 325 mmol) were slowly added, and stirred for 1 hour at 0° C. At −78° C., drops of trimethylborate (33.8 g, 325 mmol) were slowly added, and then heated to room temperature. After 2 hours of stirring, the reaction was terminated with an aqueous hydrochloride solution. The organic layer was extracted and distilled at a reduced pressure. Recrystallization in hexane was followed by filtration and drying to afford Intermediate 1-a (51 g) as a solid: yield 83percent.Into a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser fitted with a calcium chloride tube, a nitrogen inlet tube, a 300 mL isobaric dropping funnel and a thermometer, 60.0 g (0.326 mol) of dibenzothiophene and 900 mL of dehydrated THF was charged and cooled to -60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 230 mL (0.385 mol) of n-BuLi was added dropwise at -50 ° C. or less, and then the isobaric dropping funnel was washed with 150 mL of THF and added to the reaction solution. Subsequently, after the reaction was carried out at -50 ° C. or lower for 1 hour, the temperature was returned to room temperature and stirred for 4 hours. Subsequently, the mixture was again cooled to -60 ° C. or less with an acetone-dry ice bath, 45 mL (0.404 mol) of B (OMe) 3 was dropped at -45 ° C. or lower, and then the isobaric dropping funnel was washed with 150 mL of THF to give added. Subsequently, after stirring at -45 ° C. or less for 30 minutes, the acetone-dry ice bath was removed, the temperature was returned to room temperature and reacted for 20 hours to obtain a boron reaction solution.Next, 340 mL of concentrated hydrochloric acid and 860 mL of water were placed in a 3 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (not required), a 2000 mL dropping funnel and a thermometer, and then cooled in an ice bath to -5 ° C. Subsequently, the boron reaction solution was dropped at a temperature not exceeding 10 ° C., and the mixture was stirred at 10 ° C. or less for 1 hour, then returned to room temperature and stirred for 3 hours.The resulting reaction solution was transferred to a 5 L separating funnel, the organic layer was separated, and the aqueous layer was extracted three times with 600 mL of diethyl ether. Next, the organic layers were combined and extracted three times with 400 mL of a 10percent sodium hydroxide aqueous solution three times and then placed in a 3 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser, a 1000 mL dropping funnel and a thermometer , Acidified with 600 mL of glacial acetic acid, and the precipitated crystals were suction filtered. Next, the obtained crystals were washed with water until no acetic acid odor was eliminated and dried in a dryer at 60 ° C. to obtain 62.5 g (yield 83.5percent) of the objective compound.

Molecular Weight:228.08
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:1
Exact Mass:228.0416309
Monoisotopic Mass:228.0416309
Topological Polar Surface Area:68.7
Heavy Atom Count:16
Complexity:261
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes