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

HRID 729162
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 729162
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
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

9

Edukt 5

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel

3
HCID 8028TetrahydrofuranLösungsmittelHCID 8058HexaneLösungsmittelHCID 21941165TetrahydrofuranatLösungsmittel

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-6f4ac729c1dc409ba40b21ffa78b80df
Quelldatensatz
uspto-grants-1991_09
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US05051524

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