Sodium hydride → Tert-butyl 3-(4-cyanophenyl)prop-2-enoate

HRID 880398Notes

Reaction equation

HRID 880398 reaction equation
[H-].[Na+].C(OP([CH2:11][C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])(OCC)=O)C.[C:19]([C:21]1[CH:28]=[CH:27][C:24]([CH:25]=O)=[CH:23][CH:22]=1)#[N:20]>C1COCC1.CC(OC)(C)C.[NH4+].[Cl-]>[C:19]([C:21]1[CH:28]=[CH:27][C:24](/[CH:25]=[CH:11]/[C:12]([O:14][C:15]([CH3:16])([CH3:17])[CH3:18])=[O:13])=[CH:23][CH:22]=1)#[N:20]

Participants

7

Reactant 3

HCID 24758Sodium hydrideHCID 660424-CyanobenzaldehydeHCID 2773685tert-Butyl diethylphosphonoacetate

Product 1

HCID 11287649Tert-butyl 3-(4-cyanophenyl)prop-2-enoateYield 101.3%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent3×HCID 15413tert-Butyl methyl etherSolventHCID 25517Ammonium ChlorideSolvent

Procedure

A flame dried three-neck round-bottom flask equipped with a magnetic stirring bar, a thermometer, an addition funnel and a nitrogen inlet was charged with NaH (3.96 g, 94.7 mmol) and anhydrous THF (120 mL). Tert-butyl diethylphosphonoacetate (23.2 mL, 94.7 mmol) dissolved in anhydrous THF (20 mL) was added dropwise via the addition funnel over a period of 30 min. After the completion of addition, the reaction mixture was stirred at rt for another 30 min. A solution of 4-cyanobenzaldehyde (11.3 g, 86.1 mmol) dissolved in anhydrous THF (20 mL) was added to the reaction mixture dropwise via the addition funnel over a period of 30 min. After the end of the addition, the reaction mixture was stirred at rt for 1 h, then diluted with MTBE (200 mL) and sat. NH4Cl (150 mL). The organic layer was separated, washed with 25 mL of water and 25 mL of sat. NH4Cl, dried over MgSO4, filtered and evaporated to dryness to give 20.0 g title compound as a solid (100%). 1H NMR (400 MHz, CDCl3) δ ppm 1.56 (s, 9H) 6.47 (d, J=16 Hz, 1H) 7.58 (d, J=16 Hz, 1H) 7.61 (d, J=8 Hz, 2H) 7.68 (d, J=8 Hz, 2H).

Workup

  1. customA flame dried three-neck round-bottom flask
  2. customequipped with a magnetic stirring bar
  3. additionwas added dropwise via the addition funnel over a period of 30 min
  4. additionAfter the completion of addition
  5. additionwas added to the reaction mixture dropwise via the addition funnel over a period of 30 min
  6. additionAfter the end of the addition
  7. stirringthe reaction mixture was stirred at rt for 1 h
  8. customThe organic layer was separated
  9. washwashed with 25 mL of water and 25 mL of sat. NH4Cl
  10. dry with materialdried over MgSO4
  11. filtrationfiltered
  12. customevaporated to dryness

Sources & evidence

ORD record
ord-7bdebeabf5c643fd910f2f7b5bf5d3e0
Source dataset
uspto-grants-2015_03
Patent number
US08993577B2

Reaction notes

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