Beta-Nitrostyrene → Ethyl 3-nitro-2-phenylpropyl(diethoxymethyl)phosphinate

HRID 5181

Reaction equation

HRID 5181 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH2:13]([O:15][CH:16]([P:20]([CH3:25])(=[O:24])[O:21][CH2:22][CH3:23])[O:17][CH2:18][CH3:19])[CH3:14].[N+:26]([CH:29]=[CH:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)([O-:28])=[O:27].[Cl-].[NH4+]>O1CCCC1.CCCCCC>[N+:26]([CH2:29][CH:30]([C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)[CH2:25][P:20]([CH:16]([O:17][CH2:18][CH3:19])[O:15][CH2:13][CH3:14])(=[O:24])[O:21][CH2:22][CH3:23])([O-:28])=[O:27]

Participants

8

Reactant 5

HCID 7626Beta-NitrostyreneHCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 13764418Ethyl(diethoxymethyl)methylphosphinateHCID 178418339Butyllithium

Product 1

HCID 14362826Ethyl 3-nitro-2-phenylpropyl(diethoxymethyl)phosphinate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Procedure

To a solution of 5.8 g of diisopropylamine in 40 ml of tetrahydrofuran at -78° C. under an atmosphere of nitrogen are added 35.7 ml of a 1.6M solution of n-butyllithium in hexane. This solution is then stirred for a period of 10 minutes at this temperature, after which time a solution of 10.0 g of ethyl (diethoxymethyl)methylphosphinate in 20 ml of tetrahydrofuran is added. This mixture is then stirred for a period of 1 hour at -78° C. after which time a solution of 8.5 g of β-nitrostyrene in 20 ml of tetrahydrofuran is introduced. This mixture is then allowed to warm to room temperature when 40 ml of a saturated ammonium chloride solution is added. The aqueous layer is then extracted with 2×25 ml of diethyl ether and the organic extracts are combined and dried over magnesium sulphate. The solvent is then evaporated under reduced pressure and the crude product chromatographed on silica gel using ethyl acetate as an eluent to give ethyl 3-nitro-2-phenylpropyl(diethoxymethyl)phosphinate as a viscous oil, 31P=+42.3 and +42.0 ppm (CDCl3).

Workup

  1. additionis introduced
  2. additionis added
  3. extractionThe aqueous layer is then extracted with 2×25 ml of diethyl ether
  4. dry with materialdried over magnesium sulphate
  5. customThe solvent is then evaporated under reduced pressure
  6. customthe crude product chromatographed on silica gel

Sources & evidence

ORD record
ord-8eac40f644db47c7bd864d7aafcf3b39
Source dataset
uspto-grants-1993_09
Patent number
US05243062

Linked notes

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