4-Iodoanisole → N-([1,1'-biphenyl]-4-yl)-N-(4-methoxyphenyl)-[1,1':3',1''-terphenyl]-4'-amine

HRID 1021177Notes

Reaction equation

HRID 1021177 reaction equation
P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.[C:14]1([C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)[CH:19]=[CH:18][C:17]([NH:20][C:21]2[CH:26]=[CH:25][C:24]([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)=[CH:23][C:22]=2[C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)=[CH:16][CH:15]=1.I[C:46]1[CH:51]=[CH:50][C:49]([O:52][CH3:53])=[CH:48][CH:47]=1.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].CCCCCC>[C:14]1([C:39]2[CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=2)[CH:19]=[CH:18][C:17]([N:20]([C:46]2[CH:51]=[CH:50][C:49]([O:52][CH3:53])=[CH:48][CH:47]=2)[C:21]2[CH:26]=[CH:25][C:24]([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)=[CH:23][C:22]=2[C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)=[CH:16][CH:15]=1

Participants

7

Reactant 4

HCID 696764-IodoanisoleHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 86762383N-([1,1'-biphenyl]-4-yl)-[1,1':3',1''-terphenyl]-4'-amine

Product 1

HCID 86762390N-([1,1'-biphenyl]-4-yl)-N-(4-methoxyphenyl)-[1,1':3',1''-terphenyl]-4'-amineYield 94%

Reagents, catalysts & solvents 2

HCID 8058HexaneCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

Toluene (200 mL) was bubbled with nitrogen for 15 min, followed by addition of 10% t-Bu3P in hexane (2.9 mL, 1.0 mmol) and Pd2(dba)3 (1.1 g, 1.2 mmol). The mixture was bubbled with nitrogen for 15 min, then N-([1,1′-biphenyl]-4-yl)-[1,1′:3′,1″-terphenyl]-4′-amine (10.6 g, 26.5 mmol), 4-iodoanisole (11.2 g, 48.0 mmol), sodium tert-butoxide (3.5 g, 36.0 mmol) were added. The mixture was bubbled with nitrogen for 15 min and stirred for 16 h at room temperature. The reaction mixture was filtered through a silica pad and washed with toluene (containing 0.5% triethylamine). The solvent was removed in vacuo and the residue was purified by flash chromatography using 30-40% toluene/hexane (containing 0.5% triethylamine) to afford N-([1,1′-biphenyl]-4-yl)-N-(4-methoxyphenyl)-[1,1′:3′,1″-terphenyl]-4′-amine (12.5 g, 94% yield) as a white solid.

Workup

  1. customToluene (200 mL) was bubbled with nitrogen for 15 min
  2. customThe mixture was bubbled with nitrogen for 15 min
  3. customThe mixture was bubbled with nitrogen for 15 min
  4. filtrationThe reaction mixture was filtered through a silica pad
  5. washwashed with toluene (containing 0.5% triethylamine)
  6. customThe solvent was removed in vacuo
  7. customthe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-2f8558c126e34378bcd9258097a7ffb4
Source dataset
uspto-grants-2014_05
Patent number
US08716484B1

Reaction notes

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