Chlorotrimethylsilane → HCID 18403070, Verbindung

HRID 377189Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 377189
[CH2:1]([PH:5](=[O:7])[OH:6])[CH2:2][CH2:3][CH3:4].C(N(CC)CC)C.C[Si](Cl)(C)C.[CH2:20]([O:27][C:28]([CH:30]([CH2:43][CH2:44][C:45]([O:47][CH2:48][C:49]1[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=1)=[O:46])[CH2:31]P(C)(=O)OCC1C=CC=CC=1)=[O:29])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>ClCCl>[CH2:1]([P:5]([CH2:31][CH:30]([C:28]([O:27][CH2:20][C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1)=[O:29])[CH2:43][CH2:44][C:45]([O:47][CH2:48][C:49]1[CH:50]=[CH:51][CH:52]=[CH:53][CH:54]=1)=[O:46])(=[O:6])[OH:7])[CH2:2][CH2:3][CH3:4]

Komponenten

6

Edukt 4

HCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 158852182,4-Di(benzyloxycarbonyl)butyl(methyl)-O-benzylphosphinic acidHCID 178454911HCID 178454911, Verbindung

Produkt 1

HCID 18403070HCID 18403070, VerbindungAusbeute 40,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Butylphosphinic acid (2.0 g, 16 mmol) in 80 mL of dry dichloromethane was cooled to 0° C. under an atmosphere of nitrogen. Triethylamine (6.7 g, 66 mmol) was added followed by trimethylsilyl chloride (58 mL, 58 mmol, 1.0 M in dichloromethane). The mixture was stirred at 0° C. for 10 minutes and dibenzyl 2-methylenepentanedioate (2)(6.4 g, 20 mmol) in 20 mL of dichloromethane was added. The cold bath was removed and the reaction warmed to room temperature and stirred overnight. The mixture was then cooled to 0° C. and quenched by the slow addition of 5% hydrochloric acid. The dichloromethane layer was then removed and washed with 5% hydrochloric acid and with brine. The organic layer was dried (MgSO4) and evaporated to give a clear light golden liquid. The liquid was purified by flash chromatography and eluted with 3:1 hexane/ethyl acetate containing 5% acetic acid. The desired fractions were combined and evaporated to give butyl[2,4-di(benzyloxycarbonyl)butyl]phosphinic acid (3,R=n-butyl, R1=H) (2.9 g, 40%) as a clear and colorless oil. Rf0.12 (3:1, Hex./EtOAc 5% AcOH).

Aufarbeitung

  1. customThe cold bath was removed
  2. temperaturethe reaction warmed to room temperature
  3. stirringstirred overnight
  4. temperatureThe mixture was then cooled to 0° C.
  5. customquenched by the slow addition of 5% hydrochloric acid
  6. customThe dichloromethane layer was then removed
  7. washwashed with 5% hydrochloric acid and with brine
  8. dry with materialThe organic layer was dried (MgSO4)
  9. customevaporated
  10. customto give a clear light golden liquid
  11. customThe liquid was purified by flash chromatography
  12. washeluted with 3:1 hexane/ethyl acetate containing 5% acetic acid
  13. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-ba9a2206c9474e41be93a2640223114c
Quelldatensatz
uspto-grants-2000_02
Patentnummer
US06025345

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