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

HRID 1426296Notes

Reaction equation

HRID 1426296 reaction equation
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

Participants

5

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-0461e984eb1b4f898fcd9469ba40a88f
Source dataset
uspto-grants-2015_01
Patent number
US08933085B2

Reaction notes

Loading…