Diisopropylamine → Isobutyl 2-(4-fluorophenyl)-3-nitro-propyl(methyl)phosphinate

HRID 1463636Notes

Reaction equation

HRID 1463636 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH3:13][P:14]([CH3:21])(=[O:20])[O:15][CH2:16][CH:17]([CH3:19])[CH3:18].[F:22][C:23]1[CH:28]=[CH:27][C:26](/[CH:29]=[CH:30]/[N+:31]([O-:33])=[O:32])=[CH:25][CH:24]=1.[Cl-].[NH4+]>O1CCCC1.CCCCCC>[F:22][C:23]1[CH:24]=[CH:25][C:26]([CH:29]([CH2:30][N+:31]([O-:33])=[O:32])[CH2:13][P:14]([CH3:21])(=[O:20])[O:15][CH2:16][CH:17]([CH3:19])[CH3:18])=[CH:27][CH:28]=1

Participants

8

Reactant 5

HCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 4188612isobutyl P,P-dimethyl-phosphinateHCID 53816801-Fluoro-4-((1E)-2-nitroethenyl)benzeneHCID 178418339Butyllithium

Product 1

HCID 19090918Isobutyl 2-(4-fluorophenyl)-3-nitro-propyl(methyl)phosphinate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

To a solution of 8.1 g of diisopropylamine in 50 ml of dry tetrahydrofuran at -78° C. under an atmosphere of nitrogen are added 50.0 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 isobutyl P,P-dimethyl-phosphinate is added. This mixture is stirred at -78° C. for a period of 1 hour, after which time a solution of 11.1 g of trans-1-(4-fluorophenyl)-2-nitro-ethene in 50 ml of tetrahydrofuran is added. 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 purified by chromatography on silica gel using 5 parts ethyl acetate to 1 part ethanol as eluent. The fractions containing product are combined and concentrated under reduced pressure to give isobutyl 2-(4-fluorophenyl)-3-nitro-propyl-(methyl)phosphinate as a viscous oil, 31P-N.M.R. spectrum: δ=+51.0 and +50.6 ppm (CDCl3).

Workup

  1. stirringThis mixture is stirred at -78° C. for a period of 1 hour
  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 purified by chromatography on silica gel using 5 parts ethyl acetate to 1 part ethanol as eluent
  7. additionThe fractions containing product
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-95c354e2969c434cb75b03882b75248f
Source dataset
uspto-grants-1994_04
Patent number
US05300679

Reaction notes

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