p-Bromochlorobenzene → HCID 66800151, compound

HRID 1528298Notes

Reaction equation

HRID 1528298 reaction equation
[CH3:1][C:2]1([CH3:12])[CH2:11][NH:10][C@H:9]2[C@H:4]([CH2:5][CH2:6][CH2:7][CH2:8]2)[NH:3]1.Br[C:14]1[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=1.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.[H+].[B-](F)(F)(F)F.CC([O-])(C)C.[Na+].[O-]S([O-])(=O)=O.[Mg+2]>CC([O-])=O.CC([O-])=O.[Pd+2].CCOC(C)=O.O.C1(C)C=CC=CC=1>[ClH:20].[Cl:20][C:17]1[CH:18]=[CH:19][C:14]([N:10]2[C@H:9]3[C@H:4]([CH2:5][CH2:6][CH2:7][CH2:8]3)[NH:3][C:2]([CH3:12])([CH3:1])[CH2:11]2)=[CH:15][CH:16]=1

Participants

11

Reactant 6

HCID 7806p-BromochlorobenzeneHCID 24083Sulfuric acid magnesium salt (1:1)HCID 28118Tetrafluoroboric acidHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 22810137HCID 22810137, compoundHCID 23676156Sodium t-butoxide

Product 1

HCID 66800151HCID 66800151, compoundYield 92.3%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A toluene (10 ml) suspension of (4aR,8aS)-2,2-dimethyldecahydroquinoxaline (252 mg, 1.50 mmol), 1-bromo-4-chlorobenzene (345 mg, 1.80 mmol), Pd(OAc)2 (16.8 mg, 0.0748 mmol), t-Bu3P.HBF4 (21.8 mg, 0.0751 mmol), and NaOt-Bu (202 mg, 2.10 mmol) was stirred for 5 hours under reflux in a nitrogen atmosphere. The reaction solution was cooled to room temperature. Then, water (0.5 mL) and AcOEt (10 mL) were added thereto, and the mixture was stirred. MgSO4 was further added thereto, and the mixture was stirred. Then, insoluble matter was filtered through celite. The filtrate was concentrated under reduced pressure, and the obtained residue was purified by basic silica gel column chromatography (Hex-AcOEt). The obtained oil was dissolved in 1 N HCl-EtOH (3 mL), and the solvent was distilled off under reduced pressure. The deposited crystal was recrystallized from ethanol/acetone to obtain (4aS,8aR)-1-(4-chlorophenyl)-3,3-dimethyldecahydroquinoxaline hydrochloride (262 mg, yield: 55%) in a white powder form.

Workup

  1. temperatureunder reflux in a nitrogen atmosphere
  2. stirringthe mixture was stirred
  3. filtrationThen, insoluble matter was filtered through celite
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. customthe obtained residue was purified by basic silica gel column chromatography (Hex-AcOEt)
  6. dissolutionThe obtained oil was dissolved in 1 N HCl-EtOH (3 mL)
  7. distillationthe solvent was distilled off under reduced pressure
  8. customThe deposited crystal was recrystallized from ethanol/acetone

Sources & evidence

ORD record
ord-c1666a9e9a1d4ca9b05f6fcdc90b45f4
Source dataset
uspto-grants-2015_07
Patent number
US09090572B2

Reaction notes

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