Imidazole → diisopropyl (E)-3-acetoxymethyl-4-t-butyldiphenylsilyloxybut-1-enylphosphonate

HRID 1708086Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1708086
[C:1]([O:4][CH2:5][CH:6]([CH2:19][OH:20])/[CH:7]=[CH:8]/[P:9](=[O:18])([O:14][CH:15]([CH3:17])[CH3:16])[O:10][CH:11]([CH3:13])[CH3:12])(=[O:3])[CH3:2].N1C=CN=C1.[Si:26](Cl)([C:39]([CH3:42])([CH3:41])[CH3:40])([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1>C1COCC1>[C:1]([O:4][CH2:5][CH:6]([CH2:19][O:20][Si:26]([C:39]([CH3:42])([CH3:41])[CH3:40])([C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)/[CH:7]=[CH:8]/[P:9](=[O:18])([O:14][CH:15]([CH3:16])[CH3:17])[O:10][CH:11]([CH3:13])[CH3:12])(=[O:3])[CH3:2]

Komponenten

5

Edukt 3

HCID 795ImidazoleHCID 94078tert-ButyldiphenylchlorosilaneHCID 10357901diisopropyl (E)-3-acetoxymethyl-4-hydroxybut-1-enylphosphonate

Produkt 1

HCID 21765581diisopropyl (E)-3-acetoxymethyl-4-t-butyldiphenylsilyloxybut-1-enylphosphonateAusbeute 94,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a solution of diisopropyl (E)-3-acetoxymethyl-4-hydroxybut-1-enylphosphonate (3 g, 9.7 mmol ) and imidazole (1.7 g, 25 mmol) in anhydrous THF (60 ml) at 0° C. was added t-butyldiphenylsilylchloride (3.2 ml, 12.7 mmol). After stirring at room temperature for 3 h, the solvent was removed and the residue was partitioned between chloroform (100 ml) and brine (30 ml). The organic phase was dried (MgSo4), evaporated in vacuo and chromatographed on silica gel, eluting with chloroform of increasing polarity to chloroform-methanol (100:1) to give diisopropyl (E)-3-acetoxymethyl-4-t-butyldiphenylsilyloxybut-1-enylphosphonate as an oil (5 g, 94%); υmax (film) 3071, 3050, 2977, 2931, 2858, 1743, 1630, 1582, 1472,and 1425 cm-1 ; δH (CDCl3) 1.05 [9H, s, C(CH3)3 ], 1.26 (3H, d, J 6 Hz, CH3CH), 1.27 (3H, d, J 6 Hz, CH3CH), 1.32 [6H, d, J 6.3 Hz, (CH3)2CH], 1.98 (3H, s, CH3CO), 2.74 (1H, m, CH), 3.72 (2H, m, CH2), 4.22 (2H, m, CH2), 4.65 (2H, m, 2×CH(CH3)2 ], 5.76 (1H, ddd, J 1, 17 and 18 Hz, PCH=CH), 6.99 (1H, ddd, J 7, 17 and 22 Hz, PCH=CH), 7.3-7.7 (10H, m, 2×C6H5) (Found: C, 63.42; H, 8.22%. C29H43O6PSi requires C, 63.71; H, 7.93%.).

Aufarbeitung

  1. customthe solvent was removed
  2. customthe residue was partitioned between chloroform (100 ml) and brine (30 ml)
  3. customThe organic phase was dried (MgSo4)
  4. customevaporated in vacuo
  5. customchromatographed on silica gel
  6. washeluting with chloroform
  7. temperatureof increasing polarity to chloroform-methanol (100:1)

Quellen und Nachweise

ORD-Eintrag
ord-5d137eb318c046bcb6dae21e376348e4
Quelldatensatz
uspto-grants-1994_10
Patentnummer
US05356886

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