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

HRID 561071Notes

Reaction equation

HRID 561071 reaction equation
C(OP([CH2:9][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])(OCC)=O)C.[C:17]([C:19]1[CH:26]=[CH:25][C:22]([CH:23]=O)=[CH:21][CH:20]=1)#[N:18]>C1COCC1.CC(OC)(C)C.[NH4+].[Cl-]>[C:17]([C:19]1[CH:26]=[CH:25][C:22](/[CH:23]=[CH:9]/[C:10]([O:12][C:13]([CH3:14])([CH3:15])[CH3:16])=[O:11])=[CH:21][CH:20]=1)#[N:18]

Participants

6

Reactant 2

HCID 660424-CyanobenzaldehydeHCID 2773685tert-Butyl diethylphosphonoacetate

Product 1

HCID 11287649Tert-butyl 3-(4-cyanophenyl)prop-2-enoateYield 100%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 15413tert-Butyl methyl etherSolventHCID 25517Ammonium ChlorideSolvent

Procedure

A flame dried three-neck flask equipped with a thermometer, an addition funnel and a N2 inlet was charged with NaH (3.96 g, 1.1 eqs) and anhydrous THF (120 mL). With moderate stirring at RT, a suspension was formed. To this suspension was added a solution of t-butyl diethylphosphonoacetate (23.2 mL 1.1 eq.) dissolved in anhydrous THF (20 mL), dropwise via the addition funnel over a period of 30 min. The suspension turned into a clear, light yellow colored solution. An exotherm from 25° C. to 35° C. was observed during the addition. After completion of the addition, the resulting mixture was stirred at RT for another 30 min. A solution of 4-cyanobenzaldehyde (11.3 g, 86.1 mmol, 1.0 eq) dissolved in anhydrous THF (20 mL) was added to the reaction mixture dropwise via the addition funnel over a period of 30 min. An exotherm from 25° C. to 35° C. was observed. The resulting mixture was stirred at RT for 1 h. Progress of the reaction was monitored by 1H NMR. Upon completion, the reaction mixture was diluted with MTBE (200 mL) and sat. NH4Cl solution (150 mL). The organic layer was separated and washed, sequentially, with 25 mL of H2O and 25 mL of sat. NH4Cl solution. After drying over MgSO4, the organic phase was evaporated to dryness to give 20.0 g 21A as a white solid (100% yield). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.56 (s, 9H) 6.47 (d, 1H) 7.53-7.64 (m, 3H) 7.68 (d, 2H)

Workup

  1. customA flame dried three-neck flask
  2. customequipped with a thermometer, an addition funnel and a N2 inlet
  3. additionwas charged with NaH (3.96 g, 1.1 eqs) and anhydrous THF (120 mL)
  4. customa suspension was formed
  5. additionAn exotherm from 25° C. to 35° C. was observed during the addition
  6. additionAfter completion of the addition
  7. stirringthe resulting mixture was stirred at RT for another 30 min
  8. additionwas added to the reaction mixture dropwise via the addition funnel over a period of 30 min
  9. customfrom 25° C. to 35° C.
  10. stirringThe resulting mixture was stirred at RT for 1 h
  11. customThe organic layer was separated
  12. washwashed
  13. dry with materialAfter drying over MgSO4
  14. customthe organic phase was evaporated to dryness

Sources & evidence

ORD record
ord-c1d4469c963245f0a0cde75aa28906a9
Source dataset
uspto-grants-2011_11
Patent number
US08063215B2

Reaction notes

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