Ethyl Acetate → Methyl 6-cyano-2,2-diphenyl-1,3-benzodioxole-4-carboxylate

HRID 2251593Notes

Reaction equation

HRID 2251593 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:23]([O:25][CH3:26])=[O:24])[C:5]2[O:9][C:8]([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)([C:10]3[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=3)[O:7][C:6]=2[CH:22]=1.[C-:27]#[N:28].[K+].C1OCCOCCOCCOCCOCCOC1.CCOC(C)=O>C1C=CC=CC=1.CN(C=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[C:27]([C:2]1[CH:3]=[C:4]([C:23]([O:25][CH3:26])=[O:24])[C:5]2[O:9][C:8]([C:10]3[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=3)([C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=3)[O:7][C:6]=2[CH:22]=1)#[N:28]

Participants

9

Reactant 4

HCID 8857Ethyl AcetateHCID 9032Potassium CyanideHCID 2855718-Crown-6HCID 59642990Methyl 6-bromo-2,2-diphenyl-1,3-benzodioxole-4-carboxylate

Product 1

HCID 69222600Methyl 6-cyano-2,2-diphenyl-1,3-benzodioxole-4-carboxylate

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 241BenzeneSolventHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of methyl 6-bromo-2,2-diphenyl-1,3-benzodioxole-4-carboxylate (800 mg, 1.95 mmol, 1 eq.) in a mixture of 15 mL benzene and 5 mL DMF, Pd(PPh3)4 (225 mg, 0.195 mmol, 0.1 eq.), KCN (127 mg, 1.95 mmol, 1 eq.) and 18-crown-6 (415 mg, 1.56 mmol, 0.8 eq.) was added and the reaction mixture was stirred at 100° C. overnight. Then the reaction mixture was poured into a separatory funnel containing EtOAc and H2O and the aqueous phase was extracted with EtOAc (2×20 mL). The combined organic phases were washed with H2O, then saturated aqueous NaCl solution, dried over MgSO4, and evaporated under reduced pressure. Flash chromatography on silica gel (hexane/EtOAc=20:1→9:1) afforded the desired compound as a colorless solid.

Workup

  1. additionwas added
  2. additionThen the reaction mixture was poured into a separatory funnel
  3. extractionthe aqueous phase was extracted with EtOAc (2×20 mL)
  4. washThe combined organic phases were washed with H2O
  5. dry with materialsaturated aqueous NaCl solution, dried over MgSO4
  6. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-fd1943ecaacd4cf188eb7ca1a69f021d
Source dataset
uspto-grants-2008_01
Patent number
US07319101B2

Reaction notes

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