Dimethylacetamide → tert-butyl 4-((E)-2-(2,3-dihydrobenzo[1,4]dioxin-6-yl)vinyl)-2-nitrobenzoate

HRID 2191639Notes

Reaction equation

HRID 2191639 reaction equation
CN(C)C(=O)C.Br[C:8]1[CH:20]=[CH:19][C:11]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])=[C:10]([N+:21]([O-:23])=[O:22])[CH:9]=1.[CH:24]([C:26]1[CH:35]=[CH:34][C:29]2[O:30][CH2:31][CH2:32][O:33][C:28]=2[CH:27]=1)=[CH2:25].C1(CNCC2CCCCC2)CCCCC1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.C(OCC)(=O)C>[O:30]1[C:29]2[CH:34]=[CH:35][C:26](/[CH:24]=[CH:25]/[C:8]3[CH:20]=[CH:19][C:11]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])=[C:10]([N+:21]([O-:23])=[O:22])[CH:9]=3)=[CH:27][C:28]=2[O:33][CH2:32][CH2:31]1

Participants

8

Reactant 4

HCID 31374DimethylacetamideHCID 4594378Bis(cyclohexylmethyl)amineHCID 111945036-Vinyl-2,3-dihydrobenzo[b][1,4]dioxineHCID 26369829tert-Butyl 4-bromo-2-nitrobenzoate

Product 1

HCID 68962135tert-butyl 4-((E)-2-(2,3-dihydrobenzo[1,4]dioxin-6-yl)vinyl)-2-nitrobenzoateYield 39.4%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

To N,N-dimethylacetamide 24 mL solution of tert-butyl 4-bromo-2-nitrobenzoate 3.0 g were added 2,3-dihydro-6-vinylbenzo[1,4]dioxin 2.4 g, N,N-dicyclohexylmethylamine 4.0 mL and palladium acetate 0.11 g at room temperature, and it was stirred under nitrogen atmosphere at 120° C. for 3 hours. After the reaction mixture was cooled to room temperature, ethyl acetate and water were added to it, and insoluble matter was filtrated. The organic layer was separated and collected,dried over anhydrous magnesium sulfate after sequential washing with 10% citric acid aqueous solution and saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The obtained residue was refined by silica gel column chromatography [Fuji SILYSIA Chemical Ltd., PSQ100B(spherical type), eluent; hexane:ethyl acetate=10:1] to give tert-butyl 4-((E)-2-(2,3-dihydrobenzo[1,4]dioxin-6-yl)vinyl)-2-nitrobenzoate 1.5 g of yellow solid.

Workup

  1. temperatureAfter the reaction mixture was cooled to room temperature
  2. filtrationwas filtrated
  3. customThe organic layer was separated
  4. washafter sequential washing with 10% citric acid aqueous solution and saturated sodium chloride aqueous solution
  5. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-233009de849e4f3a9316bc9af1e6712b
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

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