Diethyl (cyanomethyl)phosphonate → HCID 66824380, compound

HRID 1692930Notes

Reaction equation

HRID 1692930 reaction equation
CC(C)([O-])C.[K+].[C:7]([CH2:9]P(=O)(OCC)OCC)#[N:8].O=[C:19]1[CH2:22][CH:21]([C:23]#[N:24])[CH2:20]1>C1COCC1>[C:7]([CH:9]=[C:19]1[CH2:22][CH:21]([C:23]#[N:24])[CH2:20]1)#[N:8]

Participants

5

Reactant 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 130823903-Oxocyclobutane-1-carbonitrileHCID 23665647Potassium tert-butoxide

Product 1

HCID 66824380HCID 66824380, compoundYield 71.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a solution of 1 M of potassium tert-butoxide in THF (67.4 mL) at 0° C. was added dropwise a solution of diethyl cyanomethylphosphonate (11.4 mL, 0.0706 mol) in tetrahydrofuran (100 mL, 1 mol). The reaction mixture was warmed up to room temperature and cooled to 0° C. again. To the resulting mixture, a solution of 3-oxocyclobutanecarbonitrile (6.10 g, 0.0641 mol) in tetrahydrofuran (20 mL, 0.2 mol) was added. The reaction mixture was allowed to warm up to room temperature and stirred for 2 hours. After quenching with water, the mixture was extracted with EtOAc. The combined organic layers were dried and concentrated. The residue was purified by flash silica gel column, eluting with 0-10% MeOH/dichloromethane to give the titled product (5.40 g, 71.26%). LCMS (M+Na) 141.3. 1H NMR (400 MHz, CDCl3): δ 5.30 (1H, m), 3.40 (2H, m), 3.14 (3H, m) ppm.

Workup

  1. temperaturecooled to 0° C. again
  2. temperatureto warm up to room temperature
  3. customAfter quenching with water
  4. extractionthe mixture was extracted with EtOAc
  5. customThe combined organic layers were dried
  6. concentrationconcentrated
  7. customThe residue was purified by flash silica gel column
  8. washeluting with 0-10% MeOH/dichloromethane

Sources & evidence

ORD record
ord-6f7f8309890141b9be360ba222fe7e50
Source dataset
uspto-grants-2012_04
Patent number
US08158616B2

Reaction notes

Loading…