Diphenylamine → HCID 58729313, compound

HRID 552876Notes

Reaction equation

HRID 552876 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[C:16]([CH3:25])=[C:17]([CH3:24])[C:18]([Br:23])=[C:19]([CH3:22])[C:20]=1[CH3:21].CC(C)([O-])C.[Na+]>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].P(C(C)(C)C)(C(C)(C)C)C(C)(C)C>[Br:23][C:18]1[C:17]([CH3:24])=[C:16]([CH3:25])[C:15]([N:7]([C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)=[C:20]([CH3:21])[C:19]=1[CH3:22]

Participants

5

Reactant 3

HCID 11487Diphenylamine2×HCID 74241Benzene, 1,4-dibromo-2,3,5,6-tetramethyl-HCID 23676156Sodium t-butoxide

Product 1

HCID 58729313HCID 58729313, compound

Reagents, catalysts & solvents 1

HCID 131728934HCID 131728934, compoundCatalyst

Procedure

An apparatus for working under inert conditions and exclusion of moisture is initially charged with 0.1 mol of diphenylamine, 0.4 mol of dibromodurene and 0.12 mol of sodium tert-butoxide. The catalyst used for C—N coupling is Pd2(dba)3/(t-Bu)3P=⅙ in a concentration of 1 mol % based on the amine. The reaction solution is heated at reflux until diphenylamine can no longer be detected by TLC comparison. For workup, the reaction solution is washed to neutrality and the organic phase is extracted. Afterward, the solvent is removed under reduced pressure, 200 ml of cyclohexane are added and the insoluble crystal slurry is filtered off with suction from dibromodurene. The filtrate is concentrated until crystallization commences again and chromatographed on silica gel with cyclohexane. Checking by HPLC-MS coupling (C18RP/10 μm/methanol/RT=7.06 min/99%, M+=379).

Workup

  1. temperatureThe reaction solution is heated
  2. washFor workup, the reaction solution is washed to neutrality
  3. extractionthe organic phase is extracted
  4. customAfterward, the solvent is removed under reduced pressure, 200 ml of cyclohexane
  5. additionare added
  6. filtrationthe insoluble crystal slurry is filtered off with suction from dibromodurene
  7. concentrationThe filtrate is concentrated until crystallization commences again
  8. customchromatographed on silica gel with cyclohexane

Sources & evidence

ORD record
ord-c31eaa4f13dc42959fdbc144cca1735b
Source dataset
uspto-grants-2011_05
Patent number
US07951874B2

Reaction notes

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