Ethyl Acetoacetate → HCID 68284299, compound

HRID 1527187Notes

Reaction equation

HRID 1527187 reaction equation
[CH3:1][O:2][C:3]([N:5]1[C:13]2[C:8](=[CH:9][CH:10]=[C:11](Br)[CH:12]=2)[CH:7]=[CH:6]1)=[O:4].[C:15]([O:21][CH2:22][CH3:23])(=[O:20])[CH2:16]C(C)=O.C(P(C(C)(C)C)C1C=CC=CC=1C1C=CC=CC=1C)(C)(C)C.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[CH3:1][O:2][C:3]([N:5]1[C:13]2[C:8](=[CH:9][CH:10]=[C:11]([CH2:16][C:15]([O:21][CH2:22][CH3:23])=[O:20])[CH:12]=2)[CH:7]=[CH:6]1)=[O:4]

Participants

8

Reactant 4

HCID 8868Ethyl AcetoacetateHCID 62657Potassium Phosphate, TribasicHCID 27349372-(Di-tert-butylphosphino)-2'-methyl-1,1'-biphenylHCID 68284058HCID 68284058, compound

Product 1

HCID 68284299HCID 68284299, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 6-bromo-indole-1-carboxylic acid methyl ester (1.12 g, 4.43 mmol), ethyl acetoacetate (1.23 mL, 9.74 mmol), palladium acetate (20 mg, 0.089 mmol), 2-di-tert-butylphosphino-2′-methylbiphenyl (55 mg, 0.177 mmol) and K3PO4 (2.58 g, 12.2 mmol) in toluene (6 mL) was heated at 100° C. under nitrogen overnight. The reaction was poured into water and extracted twice with EtOAc. The combined organic layers were dried over Na2SO4, filtered and concentrated. The crude material was purified by flash column chromatography on silica gel (c-hexane to c-hexane/EtOAc 93:7) to give the desired material. TLC, Rf (c-hexane/EtOAc 4:1)=0.3; MS (UPLC): 262.2 [M+H]+, 279.2 [M+NH4]+, 284.2 [M+Na]+, 523.3 [M+Na]+, 545.3 [2M+Na]+; tR (HPLC conditions f): 2.11 min.

Workup

  1. extractionextracted twice with EtOAc
  2. dry with materialThe combined organic layers were dried over Na2SO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe crude material was purified by flash column chromatography on silica gel (c-hexane to c-hexane/EtOAc 93:7)

Sources & evidence

ORD record
ord-f8432f615a4548c38d8382b640ec3335
Source dataset
uspto-grants-2015_07
Patent number
US09085555B2

Reaction notes

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