Diphenylamine → 8,9-Dihydrocyclopenta[def]phenanthrene

HRID 1670166Notes

Reaction equation

HRID 1670166 reaction equation
Br[C:2]1[CH:15]=[C:14]2[CH2:16][C:11]3[C:12]4[C:13]2=[C:4]([CH2:5][CH2:6][C:7]=4[CH:8]=[C:9](Br)[CH:10]=3)[CH:3]=1.C1(NC2C=CC=CC=2)C=CC=CC=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]>[CH:3]1[C:4]2[CH2:5][CH2:6][C:7]3[CH:8]=[CH:9][CH:10]=[C:11]4[CH2:16][C:14]([C:13]=2[C:12]=34)=[CH:15][CH:2]=1

Participants

7

Reactant 4

HCID 11487DiphenylamineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 125243672,6-dibromo-8,9-dihydro-4H-cyclopenta[def]phenanthreneHCID 23676156Sodium t-butoxide

Product 1

HCID 6057498,9-Dihydrocyclopenta[def]phenanthrene

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

The compound 2 (1 g, 1.747 mmol), diphenylamine (0.88 g, 5.241 mmol), sodium tert-butoxide (0.51 g, 0.5 mmol), Pd2(dba)3 [(tris(dibenzylidene acetone) dipalladium(0))] (0.08 g, 0.087 mmol), and tri(tert-butyl)phosphine (0.017 g, 0.087 mmol) in a 50 ml round bottom flask were dissolved with toluene (10 mL), and the reaction mixture was refluxed for 12 hours. After the reaction was terminated, the reaction solution was cooled to a room temperature and extracted with distilled water (100 ml). The combined organic layers were dried over MgSO4, concentrated, and purified by silica gel column chromatography. The eluate was concentrated and dried to give a material 1 represented by Formula 9 (10.9 g, yield: 70%).

Workup

  1. temperaturethe reaction mixture was refluxed for 12 hours
  2. customAfter the reaction was terminated
  3. extractionextracted with distilled water (100 ml)
  4. dry with materialThe combined organic layers were dried over MgSO4
  5. concentrationconcentrated
  6. custompurified by silica gel column chromatography
  7. concentrationThe eluate was concentrated
  8. customdried

Sources & evidence

ORD record
ord-712e78b1440340dd9129e3e60e9e2cf1
Source dataset
uspto-grants-2011_08
Patent number
US07990053B2

Reaction notes

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