CID 406 → Dimethyl (3-cyclohexyl-2-oxopropyl)phosphonate

HRID 261923

Reaktionsgleichung

Reaktionsgleichung von HRID 261923
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].P(=O)([O-])[O-].C([Li])CCC.C[O:18][C:19](=O)[CH2:20][CH:21]1[CH2:26][CH2:25][CH2:24][CH2:23][CH2:22]1>O1CCCC1.CCCCCC.C(O)(=O)C>[O:18]=[C:19]([CH2:20][CH:21]1[CH2:26][CH2:25][CH2:24][CH2:23][CH2:22]1)[CH2:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4]

Komponenten

8

Edukt 4

HCID 406CID 406HCID 12958Dimethyl methylphosphonateHCID 139743Cyclohexaneacetic acid, methyl esterHCID 178418339Butyllithium

Produkt 1

HCID 14302183Dimethyl (3-cyclohexyl-2-oxopropyl)phosphonate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 176Acetic AcidLösungsmittelHCID 8028TetrahydrofuranLösungsmittelHCID 8058HexaneLösungsmittel

Versuchsvorschrift

A solution of 49.6 g (0.40 mole) dimethyl methylphosphonate (Aldrich) in 500 ml dry tetrahydrofuran was cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution was added 188 ml of 2.34 M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 40 minutes at such a rate that the reaction temperature never rose above -65°. After an additional 5 minutes stirring at -78°, 31.2 g (0.20 mole) methylcyclohexylacetate was added dropwise at a rate that kept the reaction temperature less than -70° (20 minutes). After 1.0 hour at -78° the reaction mixture was allowed to warm to ambient temperature, neutralized with 25 ml acetic acid and rotary evaporated to a white gel. The gelatenous material was taken up in 75 ml water, the aqueous phase extracted with 100 ml portions of chloroform (3x), the combined organic extracts were backwashed (50 cc H 2 O), dried (MgSO4), and concentrated (water aspirator) to a crude residue and distilled, b.p. 160°-162° (0.2 mm) to give dimethyl 2-oxo-3-cyclohexylpropylphosphonate (2h).

Aufarbeitung

  1. customthe reaction temperature less than -70° (20 minutes)
  2. waitAfter 1.0 hour at -78° the reaction mixture was allowed
  3. customrotary evaporated to a white gel
  4. extractionthe aqueous phase extracted with 100 ml portions of chloroform (3x)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated (water aspirator) to a crude residue
  7. distillationdistilled

Quellen und Nachweise

ORD-Eintrag
ord-d805ae2a3b1d4b668f257981756fa8e8
Quelldatensatz
uspto-grants-1979_05
Patentnummer
US04152527

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