Triphenylphosphine → 3-(2-Chloro-4-nitro-phenoxy)-1-methyl-pyrrolidine

HRID 2186968Notes

Reaction equation

HRID 2186968 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[OH:11].[CH3:12][N:13]1[CH2:17][CH2:16][CH:15](O)[CH2:14]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O>O1CCCC1>[Cl:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[O:11][CH:15]1[CH2:16][CH2:17][N:13]([CH3:12])[CH2:14]1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 12074NitrofunginHCID 930741-Methyl-3-pyrrolidinolHCID 5462977Diethyl azodicarboxylate

Product 1

HCID 185429983-(2-Chloro-4-nitro-phenoxy)-1-methyl-pyrrolidine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2-chloro-4-nitrophenol (2.0 g) in tetrahydrofuran (60 mL) is added 1-methyl-3-pyrrolidinol (2.3 g), triphenyl phosphine (6.0 g), and diethylazodicarboxylate (3.6 mL) and the mixture is stirred at room temperature under an atmosphere of argon for 1.5 hours. The solution is then concentrated under reduced pressure, diluted with ethyl acetate, washed successively with 10% aqueous sodium hydroxide, water, saturated aqueous sodium chloride, and dried over anhydrous magnesium sulfate. The solvent is removed by evaporation under reduced pressure and the residue is chromatographed over silica gel (ethyl acetate then 10% methanol in dichloromethane is used as the eluant). Pooled product fractions are then recrystallized from hexanes to provide the desired product as a yellow solid. Using the above procedure and appropriate starting materials the following compounds were prepared:

Workup

  1. concentrationThe solution is then concentrated under reduced pressure
  2. additiondiluted with ethyl acetate
  3. washwashed successively with 10% aqueous sodium hydroxide, water, saturated aqueous sodium chloride
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customThe solvent is removed by evaporation under reduced pressure
  6. customthe residue is chromatographed over silica gel (ethyl acetate
  7. customPooled product fractions are then recrystallized from hexanes

Sources & evidence

ORD record
ord-4f9a680aeb5640228a83709d1a71104f
Source dataset
uspto-grants-2002_06
Patent number
US06407123B1

Reaction notes

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