Hydrochloric Acid → HCID 59595501, compound

HRID 630559Notes

Reaction equation

HRID 630559 reaction equation
Br[C:2]1[C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][C:13]=2[C:12]2[C:11]3[CH:10]=[CH:9][C:8]([Br:19])=[CH:7][C:6]=3[C:5]([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])([CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[C:4]=2[CH:3]=1.C([Li])CCC.C(O[B:45]1[O:49][C:48]([CH3:51])([CH3:50])[C:47]([CH3:53])([CH3:52])[O:46]1)(C)C.Cl>O1CCCC1.CO.CCCCCC.C(OCC)C>[Br:19][C:8]1[CH:9]=[CH:10][C:11]2[C:12]3[C:13]4[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=4[C:2]([B:45]4[O:46][C:47]([CH3:52])([CH3:53])[C:48]([CH3:50])([CH3:51])[O:49]4)=[CH:3][C:4]=3[C:5]([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])([CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[C:6]=2[CH:7]=1

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 59595498HCID 59595498, compoundHCID 178418339Butyllithium

Product 1

HCID 59595501HCID 59595501, compound

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-70 °C

Procedure

Under an inert atmosphere, 70.00 g (0.117 mol) of 5,9-Dibromo-7,7-dioctyl-7H-benzo[c]fluorene (M-15) was dissolved in dehydrated tetrahydrofuran (1170 mL) and dehydrated diethylether (1170 mL). To the obtained solution, 73 mL (1.6 mol/L) of a hexane solution of n-butyllithium was added dropwise at −70° C. for 30 minutes and further stirred at −70° C. for 50 minutes. Subsequently, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise at −78° C. for 10 minutes and further stirred at −78° C. for one hour. To this solution, an aqueous hydrochloric acid solution was added dropwise at room temperature for 15 minutes and the water layer was removed from the organic layer. To the organic layer, 1170 mL of distilled water was added and stirred. Thereafter, the water layer was removed and a 5% aqueous sodium hydrogen carbonate solution (1170 mL) was added and stirred. Thereafter, the water layer was removed. After distilled water (1170 mL) was added and stirred, the water layer was removed. Concentration and dehydration were performed to obtain an oily substance. The oily product was dissolved in tetrahydrofuran. To this, methanol was added to obtain a solid substance as a precipitate, which was filtrated and dried. Further, the solid substance was recrystallized from tetrahydrofuran and methanol, twice to obtain a desired compound 2-(9-Bromo-7,7-dioctyl-7H-benzo[c]fluoren-5-yl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (M-14) (57.7 g) in a yield of 76%.

Workup

  1. stirringfurther stirred at −78° C. for one hour
  2. customthe water layer was removed from the organic layer
  3. additionTo the organic layer, 1170 mL of distilled water was added
  4. stirringstirred
  5. customThereafter, the water layer was removed
  6. additiona 5% aqueous sodium hydrogen carbonate solution (1170 mL) was added
  7. stirringstirred
  8. customThereafter, the water layer was removed
  9. distillationAfter distilled water (1170 mL)
  10. additionwas added
  11. stirringstirred
  12. customthe water layer was removed
  13. concentrationConcentration and dehydration
  14. customto obtain an oily substance
  15. customto obtain a solid substance as a precipitate
  16. filtrationwhich was filtrated
  17. customdried
  18. customFurther, the solid substance was recrystallized from tetrahydrofuran and methanol

Sources & evidence

ORD record
ord-b4c95918d312451c81fe758426944b76
Source dataset
uspto-grants-2016_04
Patent number
US09315723B2

Reaction notes

Loading…