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

HRID 1426296
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HRID 1426296 반응식
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>C1COCC1>[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
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

5

반응물 3

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

생성물 1

HCID 66824450(3-{[Tert-butyl(diphenyl)silyl]oxy}cyclobutylidene)acetonitrile수율 100.1%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

To a solution of 1.0M potassium tert-butoxide in tetrahydrofuran (5.95 mL, 5.95 mmol) at 0° C. was added diethyl cyanomethylphosphonate (1.05 g, 5.95 mmol). The bath was removed and reaction allowed to warm to room temperature for 1 hour. The reaction was cooled to 0° C. and a solution of 3-{[tert-butyl(diphenyl)silyl]oxy}cyclobutanone (1.95 g, 6.01 mmol) in THF (10 mL) was added. Upon complete addition, the bath was removed and the reaction was allowed to warm to room temperature and stir overnight. The reaction solution was diluted with water and ethyl acetate. The aqueous layer was extracted with ethyl acetate three times. The combined extracts were washed with brine, dried over sodium sulfate, decanted and concentrated. The crude was purified silica gel column to give the desired product (2.07 g, 90%) as an oil. LCMS (M+H)+: 348.2.

후처리

  1. customThe bath was removed
  2. customreaction
  3. temperatureThe reaction was cooled to 0° C.
  4. additionUpon complete addition
  5. customthe bath was removed
  6. temperatureto warm to room temperature
  7. additionThe reaction solution was diluted with water and ethyl acetate
  8. extractionThe aqueous layer was extracted with ethyl acetate three times
  9. washThe combined extracts were washed with brine
  10. dry with materialdried over sodium sulfate
  11. customdecanted
  12. concentrationconcentrated
  13. customThe crude was purified silica gel column

출처 및 근거

ORD 기록
ord-0461e984eb1b4f898fcd9469ba40a88f
출처 데이터셋
uspto-grants-2015_01
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US08933085B2

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