Trimethyl borate → HCID 58251291, compound

HRID 2170451Notes

Reaction equation

HRID 2170451 reaction equation
Br[C:2]1[C:15]2[C:16]3=[C:17]4[C:12](=[CH:13][CH:14]=2)[CH:11]=[CH:10][CH:9]=[C:8]4[CH:7]=[CH:6][C:5]3=[CH:4][CH:3]=1.C([Li])CCC.B(OC)(OC)OC.[Cl:30][C:31]1[C:32](Br)=[C:33]([CH:39]=[CH:40][C:41]=1[C:42]([O:44][CH2:45][CH3:46])=[O:43])[C:34]([O:36][CH2:37][CH3:38])=[O:35].C([O-])([O-])=O.[Na+].[Na+]>C1COCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCO.C1(C)C=CC=CC=1.O>[Cl:30][C:31]1[CH:32]=[C:33]([C:34]([O:36][CH2:37][CH3:38])=[O:35])[C:39]([C:9]2[C:8]3[C:17]4=[C:16]5[C:5](=[CH:6][CH:7]=3)[CH:4]=[CH:3][CH:2]=[C:15]5[CH:14]=[CH:13][C:12]4=[CH:11][CH:10]=2)=[CH:40][C:41]=1[C:42]([O:44][CH2:45][CH3:46])=[O:43]

Participants

11

Reactant 5

HCID 8470Trimethyl borateHCID 10340Sodium CarbonateHCID 1596271-BromopyreneHCID 67151796HCID 67151796, compoundHCID 178418339Butyllithium

Product 1

HCID 58251291HCID 58251291, compoundYield 70.1%

Reagents, catalysts & solvents 5

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-75 °C

Procedure

28.9 g (103 mmol) of bromopyrene are dissolved in 275 ml of dry THF, the solution is cooled to −75° C., and 52 ml (104 mmol) of a 2 M solution of n-butyllithium are added dropwise at this temperature. The yellow suspension is stirred at −75° C. for 1 h, and 17.5 ml (155 mmol) of trimethyl borate are then added dropwise. After the mixture has been warmed to RT, 34.5 g (103 mmol) of diethyl chlorobromoterephthalate, 22 g (206 mmol) of Na2CO3, 1.2 g (1.03 mmol) of tetrakis(triphenylphosphine)palladium(0), 140 ml of H2O, 280 ml of toluene and 140 ml of EtOH are added, and the mixture is heated at the boil for 2 h. After the organic phase has been separated off, washed twice with water and dried over Na2SO4, the solvent is removed in vacuo, and the oil which remains is brought to crystallisation in heptane. Recrystallisation twice gives the product in the form of a colourless solid (33 g, 70%) and a purity of >98%, which is employed in this form in the subsequent reaction.

Workup

  1. temperatureAfter the mixture has been warmed to RT
  2. temperaturethe mixture is heated at the boil for 2 h
  3. customAfter the organic phase has been separated off
  4. washwashed twice with water
  5. dry with materialdried over Na2SO4
  6. customthe solvent is removed in vacuo
  7. customthe oil which remains is brought to crystallisation in heptane
  8. customRecrystallisation

Sources & evidence

ORD record
ord-b9ce96607e574bf8936171addfe9c457
Source dataset
uspto-grants-2015_06
Patent number
US09051233B2

Reaction notes

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