Diethyl (cyanomethyl)phosphonate → HCID 18670614, compound

HRID 1772771Notes

Reaction equation

HRID 1772771 reaction equation
CC(C)([O-])C.[K+].[C:7]([CH2:9]P(=O)(OCC)OCC)#[N:8].O=[CH:19][CH2:20][CH:21]1[CH2:26][CH2:25][N:24]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:23][CH2:22]1>C1COCC1>[C:7](/[CH:9]=[CH:19]/[CH2:20][CH:21]1[CH2:26][CH2:25][N:24]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:23][CH2:22]1)#[N:8]

Participants

5

Reactant 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 10353694tert-Butyl 4-(2-oxoethyl)piperidine-1-carboxylateHCID 23665647Potassium tert-butoxide

Product 1

HCID 18670614HCID 18670614, compoundYield 75.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a solution of 1.0 M of potassium tert-butoxide in THF (45.8 mL, 0.0458 mol) at 0° C. was added dropwise a solution of diethyl cyanomethylphosphonate (7.8 mL, 0.0480 mol) in THF (58.4 mL). The reaction was warmed to RT and then cooled to 0° C. again. To the reaction mixture was added a solution of tert-butyl 4-(2-oxoethyl)piperidine-1-carboxylate (9.91 g, 0.0436 mol) in THF (11.7 mL). The reaction was allowed to warm up to RT and stirred at RT overnight. After being quenched with water, the mixture was extracted with EtOAc. The combined organic layers were washed with brine, dried and evaporated to dryness. The crude mixture was purified on silica gel, eluting with 0 to 40% EtOAc in hexanes, to provide the desired product (8.22 g, 75.3%). LCMS calculated for C14H22N2O2Na(M+Na)+: m/z=273.2; Found: 273.0.

Workup

  1. temperaturecooled to 0° C. again
  2. temperatureto warm up to RT
  3. customAfter being quenched with water
  4. extractionthe mixture was extracted with EtOAc
  5. washThe combined organic layers were washed with brine
  6. customdried
  7. customevaporated to dryness
  8. customThe crude mixture was purified on silica gel
  9. washeluting with 0 to 40% EtOAc in hexanes

Sources & evidence

ORD record
ord-6df839721215443780017c69915d381b
Source dataset
uspto-grants-2016_02
Patent number
US09249145B2

Reaction notes

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