Sodium Carbonate → HCID 86625361, compound

HRID 1986222Notes

Reaction equation

HRID 1986222 reaction equation
C([N-]C(C)C)(C)C.[Li+].[CH3:9][O:10][C:11]([C:13]1[C:21]2[CH:20]=[CH:19][S:18][C:17]=2[CH:16]=[CH:15][CH:14]=1)=[O:12].B(OC(C)C)(OC(C)C)OC(C)C.C([O-])([O-])=O.[Na+].[Na+].[Cl:41][C:42]1[N:47]=[C:46](Cl)[CH:45]=[CH:44][N:43]=1>C1COCC1.ClCCl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:9][O:10][C:11]([C:13]1[C:21]2[CH:20]=[C:19]([C:44]3[CH:45]=[CH:46][N:47]=[C:42]([Cl:41])[N:43]=3)[S:18][C:17]=2[CH:16]=[CH:15][CH:14]=1)=[O:12]

Participants

10

Reactant 5

HCID 10340Sodium CarbonateHCID 21531Triisopropyl borateHCID 775312,4-DichloropyrimidineHCID 2724682Lithium diisopropylamideHCID 13448678Methyl 1-benzothiophene-4-carboxylate

Product 1

HCID 86625361HCID 86625361, compoundYield 51%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Lithium diisopropylamide (5.70 mL, 2 M in THF) is added dropwise to a stirred solution of benzo[b]thiophene-4-carboxylic acid methyl ester (2.00 g, 10.4 mmol) and triisopropyl borate (2.63 mL, 11.4 mmol) in anhydrous THF (20 mL) at −78° C. under nitrogen. Upon the completion of the addition, the mixture is allowed to warm slowly over 1 hour to ambient temperature where it is stirred for another 1 hour. Aqueous Na2CO3 solution (2 M, 15.6 mL) is added to the mixture, followed by the addition of 1,1′-bis(diphenylphosphino)ferrocene (318 mg, 0.570 mmol), palladium(II) acetate (129 mg, 0.570 mmol) and 2,4-dichloropyrimidine (1.46 g, 10.4 mmol). The reaction mixture is heated to reflux for 16 hours. At ambient temperature THF is evaporated off, the aqueous layer is extracted with CHCl3 (100 mL×2) and the combined layers are concentrated to give a dark solid. The solid is dissolved in dichloromethane and purified by chromatography on silica gel, eluting with dichloromethane in hexanes 50-100%, to give the title compound as a yellowish solid (1.60 g, 51% yield).

Workup

  1. additionUpon the completion of the addition
  2. temperatureto warm slowly over 1 hour to ambient temperature where it
  3. temperatureThe reaction mixture is heated
  4. temperatureto reflux for 16 hours
  5. customAt ambient temperature THF is evaporated off
  6. extractionthe aqueous layer is extracted with CHCl3 (100 mL×2)
  7. concentrationthe combined layers are concentrated
  8. customto give a dark solid
  9. custompurified by chromatography on silica gel
  10. washeluting with dichloromethane in hexanes 50-100%

Sources & evidence

ORD record
ord-9215c64f15844f0d9fc004d9b8aa4cc9
Source dataset
uspto-grants-2009_06
Patent number
US07547691B2

Reaction notes

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