Diphenylamine → HCID 22995277, compound

HRID 1176959Notes

Reaction equation

HRID 1176959 reaction equation
[C:1]1([NH:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:15]1[CH:20]=[CH:19][C:18]([C:21]([C:23]([C:25]2[CH:30]=[CH:29][C:28](Br)=[CH:27][CH:26]=2)=[O:24])=[O:22])=[CH:17][CH:16]=1.C[C:33]([O-])([CH3:35])[CH3:34].[Na+].[NH4+:38].[Cl-]>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].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2]>[C:8]1([N:7]([C:15]2[CH:20]=[CH:19][C:18]([C:21]([C:23]([C:25]3[CH:30]=[CH:29][C:28]([N:38]([C:34]4[CH:33]=[CH:35][CH:13]=[CH:8][CH:9]=4)[C:1]4[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=4)=[CH:27][CH:26]=3)=[O:24])=[O:22])=[CH:17][CH:16]=2)[C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1

Participants

8

Reactant 4

HCID 11487DiphenylamineHCID 25517Ammonium ChlorideHCID 964304,4'-DibromobenzilHCID 23676156Sodium t-butoxide

Product 1

HCID 22995277HCID 22995277, compoundYield 39%

Reagents, catalysts & solvents 3

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
120 °C

Procedure

A schlenk tube was charged with diphenylamine (0.97 g, 5.7 mmol), 4,4′-dibromobenzil (1.0 g, 2.7 mmol), Pd2(dba)3 (0.12 g, 0.13 mmol), dppf (0.15 g, 0.27 mmol), and NaOtBu (1.04 g, 11 mmol) in 50 mL of dry toluene. The reaction mixture was refluxed at 120° C. for 2 days under an argon atmosphere. The reaction mixture was then poured into a saturated NH4Cl aqueous solution and extracted with CH2Cl2. The combined organic layer was dried over anhydrous MgSO4 and the solvent was removed under reduced pressure. The product was purified by column chromatography (silica gel, dichloromethane:hexanes=2:1 (v/v)) to give a yellow solid (0.58 g, 39%). 1H NMR (300 MHz, CDCl3, δ): 7.67 (d, J=8.8 Hz, 4H), 7.07-7.33 (m, 20H), 7.01 (d, J=8.8 Hz). 13C{1H} NMR (75 MHz, CDCl3, δ): 193.82, 151.32, 146.62, 131.54, 130.50, 129.50, 125.72, 124.31, 119.87. IR (cm−1): 3059, 3055, 1646, 1636, 1585, 1489, 1311, 1278, 1172. Anal. Calcd for C38H28N2O2: C, 83.80; H, 5.18; N, 5.14. Found: C, 84.12; H, 5.44; N, 5.02.

Workup

  1. extractionextracted with CH2Cl2
  2. dry with materialThe combined organic layer was dried over anhydrous MgSO4
  3. customthe solvent was removed under reduced pressure
  4. customThe product was purified by column chromatography (silica gel, dichloromethane:hexanes=2:1 (v/v))

Sources & evidence

ORD record
ord-99a4e2ef0ed14a559d90012c1feb5327
Source dataset
uspto-grants-2010_11
Patent number
US07842830B2

Reaction notes

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