Nitrogen → HCID 67128437, compound

HRID 1189405Notes

Reaction equation

HRID 1189405 reaction equation
N#N.Br[C:4]1[CH:5]=[C:6]([C:10]2([CH3:15])[O:14][CH2:13][CH2:12][O:11]2)[CH:7]=[CH:8][CH:9]=1.C(P(C(C)(C)C)C1C=CC=CC=1C1C=CC=CC=1C)(C)(C)C.O.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[C:47]([O:53][CH2:54][CH3:55])(=[O:52])[CH2:48]C(C)=O>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[CH2:54]([O:53][C:47](=[O:52])[CH2:48][C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([C:10]2([CH3:15])[O:14][CH2:13][CH2:12][O:11]2)[CH:5]=1)[CH3:55]

Participants

9

Reactant 5

HCID 947NitrogenHCID 8868Ethyl AcetoacetateHCID 27349372-(Di-tert-butylphosphino)-2'-methyl-1,1'-biphenylHCID 109992182-(3-Bromophenyl)-2-methyl-1,3-dioxolaneHCID 22031701Potassium phosphate, tribasic, monohydrate

Product 1

HCID 67128437HCID 67128437, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

In a flame dried round-bottomed flask equipped with a magnetic stir bar and under inert atmosphere (N2), a suspension of 2-(3-bromo-phenyl)-2-methyl-[1,3]dioxolane (3.620 g, 14.89 mmol), 2-di-t-butylphosphino-2′-methylbiphenyl (931 mg, 2.98 mmol), tri-potassiumphosphate monohydrate (11.063 g, 52.12 mmol) and palladium(II)acetate (334 mg, 1.49 mmol) in toluene (74 mL) was treated with ethyl acetoacetate (2.45 mL, 19.36 mmol). The reaction mixture was heated at 90° C. for 2 h followed by 4 h at 100° C. The reaction mixture was cooled to rt, water (100 mL) was added and the mixture was stirred for 30 min at rt. The org. layers was separated and washed twice with 5% aq. NaCl (50 mL), brine (50 mL) dried over Na2SO4, filtered, and the solvent was removed under reduced pressure. Purification of the residue by FC (4:1 hept-EA) gave the title compound as an orange oil. TLC: rf (4:1 hept-EA)=0.37. LC-MS-conditions 02: tR=0.96 min, [M+H]+=251.21.

Workup

  1. temperatureThe reaction mixture was cooled to rt
  2. customlayers was separated
  3. washwashed twice with 5% aq. NaCl (50 mL), brine (50 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. customthe solvent was removed under reduced pressure
  7. customPurification of the residue by FC (4:1 hept-EA)

Sources & evidence

ORD record
ord-2bd6cbbc396a4af098aa4a61dea08a20
Source dataset
uspto-grants-2014_03
Patent number
US08674111B2

Reaction notes

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