Benzaldehyde → 2,4-Di(prop-1-en-2-yl)dibenzo[b,d]thiophen-3-amine

HRID 1750926Notes

Reaction equation

HRID 1750926 reaction equation
Br[C:2]1[C:14]([NH2:15])=[C:13](Br)[C:5]2[S:6][C:7]3[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=3[C:4]=2[CH:3]=1.[CH3:17][C:18]1(C)[C:22](C)(C)OB(C(C)=C)O1.[CH:29](=O)[C:30]1C=CC=C[CH:31]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>C(OCC)(=O)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O.C1(C)C=CC=CC=1>[CH2:17]=[C:18]([C:2]1[C:14]([NH2:15])=[C:13]([C:30]([CH3:31])=[CH2:29])[C:5]2[S:6][C:7]3[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=3[C:4]=2[CH:3]=1)[CH3:22]

Participants

9

Reactant 4

HCID 240BenzaldehydeHCID 62657Potassium Phosphate, TribasicHCID 109974264,4,5,5-Tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolaneHCID 584010402,4-Dibromodibenzo[b,d]thiophen-3-amine

Product 1

HCID 584009962,4-Di(prop-1-en-2-yl)dibenzo[b,d]thiophen-3-amineYield 95%

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a degassed toluene (200 mL), 2,4-dibromodibenzo[b,d]thiophen-3-amine (12.15 g, 34.0 mmol), 4,4,5,5-tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolane (17.15 g, 102 mmol), benzaldehyde (3.61 g, 34.0 mmol), potassium phosphate (23.51 g, 102 mmol) dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (1.676 g, 4.08 mmol) and Pd2(dba)3 (0.935 g, 1.021 mmol) and water (20 mL) were sequentially added. The solution was refluxed for overnight in an atmosphere of nitrogen and then allowed to cool to room temperature. The reaction was diluted with ethyl acetate and the organic phase was separated from the aqueous phase. The organic phase was dried over sodium sulfate and the solvent was removed under vacuum. The product was chromatographed using silica gel with ethylacetate and hexanes as the eluent. The solvent was removed to give the title compound (9.0, 95%).

Workup

  1. temperatureThe solution was refluxed for overnight in an atmosphere of nitrogen
  2. customthe organic phase was separated from the aqueous phase
  3. dry with materialThe organic phase was dried over sodium sulfate
  4. customthe solvent was removed under vacuum
  5. customThe product was chromatographed
  6. customThe solvent was removed

Sources & evidence

ORD record
ord-03171f66983c42f68f9f6cbdfa382131
Source dataset
uspto-grants-2015_10
Patent number
US09156870B2

Reaction notes

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