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Diisopropylamine → isobutyl P-(3-t-butoxycarbonylamino-2-oxo-propyl)-P-(methyl)-phosphinate

HRID 865846
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 865846
C(N[CH:5]([CH3:7])C)(C)C.C([Li])CCC.[CH3:13][P:14]([CH3:21])(=[O:20])[O:15][CH2:16][CH:17]([CH3:19])[CH3:18].[C:22]([O:26][C:27]([NH:29]NCC(OC)=O)=[O:28])([CH3:25])([CH3:24])[CH3:23].C(=O)(O)[O-:37].[Na+]>O1CCCC1.CCCCCC.C(O)(=O)C>[C:22]([O:26][C:27]([NH:29][CH2:7][C:5](=[O:37])[CH2:13][P:14]([CH3:21])(=[O:20])[O:15][CH2:16][CH:17]([CH3:19])[CH3:18])=[O:28])([CH3:23])([CH3:24])[CH3:25]
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Komponenten

9

Edukt 5

HCID 7912DiisopropylamineHCID 516892Sodium BicarbonateHCID 4188612isobutyl P,P-dimethyl-phosphinateHCID 12031831Hydrazinecarboxylic acid, 2-(2-methoxy-2-oxoethyl)-, 1,1-dimethylethyl esterHCID 178418339Butyllithium

Produkt 1

HCID 23374770
isobutyl P-(3-t-butoxycarbonylamino-2-oxo-propyl)-P-(methyl)-phosphinate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 176Acetic AcidLösungsmittelHCID 8028TetrahydrofuranLösungsmittel3×HCID 8058HexaneLösungsmittel

Versuchsvorschrift

To a solution of 6.1 g of diisopropylamine in 25 ml of dry tetrahydrofuran at 0° under an atmosphere of nitrogen are added 37.5 ml of a 1.6M solution of n-butyllithium in hexane. This solution is stirred for a period of 10 minutes and then cooled to -78°. To this is added, via a syringe, a solution of 9.0 g of isobutyl P,P-dimethyl-phosphinate in 50 ml of dry tetrahydrofuran and the mixture is stirred at -78° for a period of 1 hour. To this is then added a solution of 1.9 g of methyl N-tert.-butoxycarbonylaminoglycinate in 25 ml of dry tetrahydrofuran and the reaction mixture is allowed to warm to room temperature and is stirred for a period of 1 hour. 3 ml of glacial acetic acid are then introduced, followed by 50 ml of saturated sodium bicarbonate solution, and the aqueous layer is extracted twice with 100 ml of ether. The organic extract is dried over magnesium sulphate and concentrated under reduced pressure. The residue is chromatographed on silica gel using ethyl acetate as eluent. There is obtained isobutyl P-(3-t-butoxycarbonylamino-2-oxo-propyl)-P-(methyl)-phosphinate, m.p. 65°-68°, 31P-NMR spectrum: δ=+44.9 ppm (CDCl3).

Aufarbeitung

  1. temperaturecooled to -78°
  2. additionTo this is added, via a syringe
  3. stirringis stirred for a period of 1 hour
  4. extractionthe aqueous layer is extracted twice with 100 ml of ether
  5. extractionThe organic extract
  6. dry with materialis dried over magnesium sulphate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue is chromatographed on silica gel

Quellen und Nachweise

ORD-Eintrag
ord-2de8c33a3a894eb4bf2a2baf38686234
Quelldatensatz
uspto-grants-1996_10
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US05567840

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