Triphenylphosphine → HCID 4176481, compound

HRID 1510187Notes

Reaction equation

HRID 1510187 reaction equation
C([Mg]Br)C.[Cl-].[CH:6]([C:9]1[CH:14]=[CH:13][CH:12]=[C:11](C(C)C)[C:10]=1[NH+]1CCN(C2C(C(C)C)=CC=CC=2C(C)C)C1)(C)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Cl[C:55]1[CH:60]=[CH:59][CH:58]=[CH:57][C:56]=1[O:61][CH3:62].C1(C)C=CC=CC=1[Mg]Br.C(C(C(C([O-])=O)O)O)([O-])=O.[K+].[Na+].ClC1C=CC=C(C(OO)=O)C=1>C1COCC1>[CH3:62][O:61][C:56]1[CH:57]=[CH:58][CH:59]=[CH:60][C:55]=1[C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=1[CH3:6]

Participants

9

Reactant 7

HCID 11776TriphenylphosphineHCID 130112-ChloroanisoleHCID 70297m-Chloroperbenzoic acidHCID 9855836Potassium sodium tartarateHCID 184547821,3-BIS(2,6-DIISOPROPYLPHENYL)imidazoLIDINIUM-CHLORIDEHCID 178418443HCID 178418443, compoundHCID 178424303HCID 178424303, compound

Product 1

HCID 4176481HCID 4176481, compoundYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A THF solution of ethylmagnesium bromide (0.324 mL, 1.08 M, 0.35 mmol) was added to FeF3.3H2O (8.34 mg, 0.05 mmol) and 1,3-bis(2,6-diisopropylphenyl)imidazolinium chloride (63.8 mg, 0.15 mmol) and triphenylphosphine (13.1 mg, 0.05 mmol) at 0° C. under argon atmosphere. The following process was also performed under argon atmosphere. After stirring for six hours at room temperature, 1-chloro-2-methoxybenzene (142.6 mg, 1.0 mmol) and a THF solution of o-tolylmagnesium bromide (1.88 mL, 0.80 M, 1.5 mmol) was added to the mixture. The mixture was reacted at 60° C. for 24 hours, and then at 80° C. for 12 hours. After cooled to the ambient temperature, 2.0 mL of saturated sodium potassium tartrate aqueous solution was added to the reaction mixture. The water layer was extracted five times using Et2O. The total organic extract was filtrated by Florisil pad (100-200 mesh, Nacalai Tesque, Inc.). After removing the solvent under reduced pressure, the crude product was dissolved in CH2Cl2 (1.0 mL). Then, m-chloroperbenzoic acid (MCPBA) (0.06 mmol) was added at room temperature, and the reaction mixture was stirred for 30 minutes. After removing the solvent under reduced pressure, the crude product was purified by silica gel chromatography (toluene=15, 30, 50% in hexane), thereby obtaining the above compound, which was a white solid (0.188 g, yield=95%, purity=>99% (GC analysis)).

Workup

  1. customThe mixture was reacted at 60° C. for 24 hours
  2. waitat 80° C. for 12 hours
  3. additionwas added to the reaction mixture
  4. extractionThe water layer was extracted five times
  5. extractionThe total organic extract
  6. filtrationwas filtrated by Florisil pad (100-200 mesh, Nacalai Tesque, Inc.)
  7. customAfter removing the solvent under reduced pressure
  8. dissolutionthe crude product was dissolved in CH2Cl2 (1.0 mL)
  9. stirringthe reaction mixture was stirred for 30 minutes
  10. customAfter removing the solvent under reduced pressure
  11. customthe crude product was purified by silica gel chromatography (toluene=15, 30, 50% in hexane)
  12. customobtaining the above compound, which

Sources & evidence

ORD record
ord-f617bbb428c94e8fa4886cb5039e6ace
Source dataset
uspto-grants-2012_07
Patent number
US08211820B2

Reaction notes

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