Tris(1,1-dimethylethyl)phosphine → N-(3-(1,3-dioxolan-2-yl)phenyl)dibenzo[b,d]thiophen-4-amine

HRID 2408320Notes

Reaction equation

HRID 2408320 reaction equation
Br[C:2]1[C:7]2[S:8][C:9]3[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=3[C:6]=2[CH:5]=[CH:4][CH:3]=1.[CH2:15]1[O:26][CH:18]([C:19]2[CH:24]=[CH:23][CH:22]=[C:21]([NH2:25])[CH:20]=2)[O:17][CH2:16]1.CC(C)([O-])C.[Na+].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[O:17]1[CH2:16][CH2:15][O:26][CH:18]1[C:19]1[CH:20]=[C:21]([NH:25][C:2]2[C:7]3[S:8][C:9]4[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=4[C:6]=3[CH:5]=[CH:4][CH:3]=2)[CH:22]=[CH:23][CH:24]=1

Participants

7

Reactant 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 4583524-BromodibenzothiopheneHCID 70203623-(1,3-Dioxolan-2-yl)anilineHCID 23676156Sodium t-butoxide

Product 1

HCID 58028499N-(3-(1,3-dioxolan-2-yl)phenyl)dibenzo[b,d]thiophen-4-amine

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent2×

Procedure

A clean and dry 1000 ml round bottom flask equipped with a reflux condenser, magnetic stir bar, and thermometer with adapter was prepared and purged with nitrogen. A solution of 4-bromodibenzo[b,d]thiophene (RS-1-170, 10.7 g, 0.0407 mol) in anhydrous toluene (500.0 ml) was then prepared and transferred to the reaction flask via cannula. 3-aminobenzaldehyde ethylene acetal (8.1 g, 0.0488 mol) was added by syringe. The reaction solution was purged with a strong nitrogen flow for 20 minutes. Sodium tert-butoxide (5.86 g, 0.0610 mol) and Pd2dba3 (1.10 g, 0.0012 mol) were then added manually, followed by the addition of tri-tert-butylphosphine (0.65 g, 0.0032 mol) in toluene (−10 ml) via syringe. The vessel was heated to reflux for approximately 2 hours. The reaction was then cooled to room temperature and filtered through a Celite and silica gel pad. Solvent was removed by rotary evaporation. The crude material was dissolved in a 2:1 hexane/ethyl acetate solution purified by flash column chromatography using a gradient elution system of ethyl acetate/hexane. This provided pure product confirmed by NMR.

Workup

  1. customA clean and dry 1000 ml round bottom flask
  2. customequipped with a reflux condenser, magnetic stir bar
  3. customthermometer with adapter was prepared
  4. custompurged with nitrogen
  5. customThe reaction solution was purged with a strong nitrogen flow for 20 minutes
  6. temperatureThe vessel was heated
  7. temperatureto reflux for approximately 2 hours
  8. filtrationfiltered through a Celite and silica gel pad
  9. customSolvent was removed by rotary evaporation
  10. dissolutionThe crude material was dissolved in a 2:1 hexane/ethyl acetate solution
  11. custompurified by flash column chromatography

Sources & evidence

ORD record
ord-990ece72241d409e881f4c5bad77a5c8
Source dataset
uspto-grants-2014_08
Patent number
US08815639B2

Reaction notes

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