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

HRID 729162
Notes
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Reaction equation

HRID 729162 reaction equation
C(N[CH:5]([CH3:7])[CH3:6])(C)C.[CH2:8]([Li])CCC.[CH3:13][P:14]([CH3:17])(=[O:16])[O-:15].[Cl:18][C:19]1[CH:24]=[CH:23][C:22]([CH:25]=[CH:26][N+:27]([O-:29])=[O:28])=[CH:21][CH:20]=1.[Cl-].[NH4+]>O1CCCC1C([O-])=O.CCCCCC.O1CCCC1>[Cl:18][C:19]1[CH:20]=[CH:21][C:22]([CH:25]([CH2:26][N+:27]([O-:29])=[O:28])[CH2:13][P:14]([CH3:17])(=[O:15])[O:16][CH2:6][CH:5]([CH3:7])[CH3:8])=[CH:23][CH:24]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

9

Reactant 5

HCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 95339p-Chloro-beta-nitrostyreneHCID 22292143DimethylphosphinateHCID 178418339Butyllithium

Product 1

HCID 10336939Isobutyl 2-(4-chlorophenyl)-3-nitro-propyl(methyl)phosphinate

Reagents, catalysts & solvents

3
HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolventHCID 21941165TetrahydrofuranatSolvent

Procedure

To a solution of 1.62 g of diisopropylamine in 20 ml of dry tetrahydrofuranat -78° C. under an atmosphere of nitrogen are added 10.0 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 2.0 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 2.45 g of tran-1-(4-chlorophenyl)-2-nitro-ethene in 20 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 ethylacetate to 1 part ethanol as eluent. The fractions containing product are combined and concentrated under reduced pressure to give isobutyl 2-(4-chlorophenyl)-3-nitro-propyl-(methyl)phosphinate as a viscous oil; 31P N.M.R. spectrum: δ=+50.5 and +50.1 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 ethylacetate to 1 part ethanol as eluent
  7. additionThe fractions containing product
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-6f4ac729c1dc409ba40b21ffa78b80df
Source dataset
uspto-grants-1991_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05051524

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes