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Diethyl (cyanomethyl)phosphonate → (3-{[Tert-butyl(diphenyl)silyl]oxy}cyclobutylidene)acetonitrile

HRID 1692947
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Reaktionsgleichung

Reaktionsgleichung von HRID 1692947
CC(C)([O-])C.[K+].[C:7]([CH2:9]P(=O)(OCC)OCC)#[N:8].[Si:18]([O:35][CH:36]1[CH2:39][C:38](=O)[CH2:37]1)([C:31]([CH3:34])([CH3:33])[CH3:32])([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>O1CCCC1>[Si:18]([O:35][CH:36]1[CH2:37][C:38](=[CH:9][C:7]#[N:8])[CH2:39]1)([C:31]([CH3:33])([CH3:34])[CH3:32])([C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

5

Edukt 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 23665647Potassium tert-butoxideHCID 668245053-((tert-Butyldiphenylsilyl)oxy)cyclobutanone

Produkt 1

HCID 66824450(3-{[Tert-butyl(diphenyl)silyl]oxy}cyclobutylidene)acetonitrileAusbeute 74,7 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028Tetrahydrofuran
Lösungsmittel
2×

Versuchsvorschrift

To 1.0 M of potassium tert-butoxide in tetrahydrofuran (1.2 mL) was added dropwise, at 0° C., diethyl cyanomethylphosphonate (0.19 mL, 0.0012 mol). The reaction was warmed to rt and 30 min later cooled to 0° C. again. To the reaction mixture was added a solution of 3-[tert-butyl(diphenyl)silyl]oxycyclobutanone (0.25 g, 0.00077 mol) in THF (5 mL). The reaction was allowed to warm up to rt gradually and stirred at rt for 2 h. The reaction was quenched with saturated aq. NH4Cl, extracted with EtOAc. The combined organic layers were washed with brine, dried over MgSO4, concentrated. The resultant residue was purified with Combiflash (silica gel, 0-20% EtOAc/Hex) to give the desired product (0.2 g) as colorless oil. LCMS calculated for C22H26NOSi(M+H)+: 348.1 Found: 348.3.

Aufarbeitung

  1. temperaturelater cooled to 0° C. again
  2. temperatureto warm up to rt gradually
  3. customThe reaction was quenched with saturated aq. NH4Cl
  4. extractionextracted with EtOAc
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated
  8. customThe resultant residue was purified with Combiflash (silica gel, 0-20% EtOAc/Hex)

Quellen und Nachweise

ORD-Eintrag
ord-6bf4010a5fcb4c268e8ddef72f7e11d8
Quelldatensatz
uspto-grants-2012_04
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08158616B2

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