Diphenylamine → HCID 58400784, compound

HRID 1877718Notes

Reaction equation

HRID 1877718 reaction equation
Br[C:2]1[S:6][C:5]2[C:7]3[CH:11]=[C:10](Br)[S:9][C:8]=3[C:13]3[CH:17]=[C:16](Br)[S:15][C:14]=3[C:4]=2[CH:3]=1.[C:19]1([NH:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.[C:32](O[Na])([CH3:35])([CH3:34])C.C(P([C:47]([CH3:50])([CH3:49])C)C(C)(C)C)(C)(C)C>C1(C)C(C)=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2].O>[C:26]1([N:25]([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)[C:2]2[S:6][C:5]3[C:7]4[CH:11]=[C:10]([N:25]([C:19]5[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=5)[C:26]5[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=5)[S:9][C:8]=4[C:13]4[CH:17]=[C:16]([N:25]([C:34]5[CH:32]=[CH:35][CH:49]=[CH:47][CH:50]=5)[C:19]5[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=5)[S:15][C:14]=4[C:4]=3[CH:3]=2)[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1

Participants

8

Reactant 4

HCID 11487DiphenylamineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 58400797HCID 58400797, compoundHCID 178418730sodium 2-methylpropan-2-olate

Product 1

HCID 58400784HCID 58400784, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 7237O-XyleneSolvent

Procedure

Under a nitrogen atmosphere, 2,5,8-tribromobenzo[1,2-b:3,4-b′:5,6-b″]trithiophene (33) (500 mg, 1.04 mmol) obtained in Example 4, diphenyl amine (0.78 g, 4.66 mmol) and tertiary butoxy sodium (0.39 g, 4.0 mmol) were suspended in xylene (10 mL) and degassed by Ar bubbling for 30 minutes. Pd(OAc)2 (2.3 mg, 0.01 mmol) and tri(tert-butyl) phosphine (10 mg) were added and heated at a reflux temperature for 34 hours. After completion of the reaction, water (10 mL) was added. The mixture was extracted with chloroform, washed and dried over anhydrous magnesium sulfate, and a solvent was distilled away under reduced pressure. The residue was dissolved in methylene chloride, reprecipitated from acetonitrile. The precipitated solid substance was obtained by filtration, washed with water (50 mL) and dried under reduced pressure. Vacuum sublimation purification was performed to obtain a light yellow substance (300 mg, 39%).

Workup

  1. customdegassed by Ar
  2. custombubbling for 30 minutes
  3. temperatureheated at a reflux temperature for 34 hours
  4. additionwas added
  5. extractionThe mixture was extracted with chloroform
  6. washwashed
  7. dry with materialdried over anhydrous magnesium sulfate
  8. distillationa solvent was distilled away under reduced pressure
  9. dissolutionThe residue was dissolved in methylene chloride
  10. customreprecipitated from acetonitrile
  11. customThe precipitated solid substance was obtained by filtration
  12. washwashed with water (50 mL)
  13. customdried under reduced pressure
  14. customVacuum sublimation purification
  15. customto obtain a light yellow substance (300 mg, 39%)

Sources & evidence

ORD record
ord-ba765799c927428392760c905a6ede2d
Source dataset
uspto-grants-2012_11
Patent number
US08313671B2

Reaction notes

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