2-Aminobiphenyl → N-([1,1'-biphenyl]-2-yl)-N-(4-methoxyphenyl)-[1,1'-biphenyl]-2-amine

HRID 929277

反応式

HRID 929277 の反応式
C1(P(C2CCCCC2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[C:14]2[C:19](OC)=[CH:18][CH:17]=[CH:16][C:15]=2OC)CCCCC1.[C:30]1([C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[C:31]([NH2:36])=[CH:32][CH:33]=[CH:34][CH:35]=1.IC1C=CC=CC=1C1C=CC=CC=1.CC(C)([O-])C.[Na+].I[C:63]1[CH:68]=[CH:67][C:66]([O:69][CH3:70])=[CH:65][CH:64]=1.C(=O)([O-])[O-].[K+].[K+].C1OCCOCCOCCOCCOCCOC1>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].[Cu]>[C:14]1([C:9]2[CH:8]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:15]=[CH:16][CH:17]=[CH:18][C:19]=1[N:36]([C:63]1[CH:68]=[CH:67][C:66]([O:69][CH3:70])=[CH:65][CH:64]=1)[C:31]1[C:30]([C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)=[CH:35][CH:34]=[CH:33][CH:32]=1

参加物

10

反応物 7

HCID 70152-AminobiphenylHCID 11430Potassium CarbonateHCID 2855718-Crown-6HCID 696764-IodoanisoleHCID 750251,1'-Biphenyl, 2-iodo-HCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 23676156Sodium t-butoxide

生成物 1

HCID 118006474N-([1,1'-biphenyl]-2-yl)-N-(4-methoxyphenyl)-[1,1'-biphenyl]-2-amine収率 721.2%

試薬・触媒・溶媒 2

HCID 23978Copper触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒

実験手順

Toluene (100 mL) was bubbled with nitrogen for 15 min, followed by the addition of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (1.0 g, 2.4 mmol) and Pd2(dba)3 (0.5 g, 0.6 mmol). The mixture was bubbled with nitrogen for 15 min, then [1,1′-biphenyl]-2-amine (3.4 g, 20.0 mmol), 2-iodobiphenyl (3.5 mL, 20.0 mmol), and sodium tert-butoxide (3.8 g, 40.0 mmol) were added. The mixture was bubbled with nitrogen for 15 min and refluxed for 21 h. After cooling, the reaction mixture was filtered through a silica pad and washed with 50% DCM/hexane. The solvent was removed in vacuo. The residue was dissolved in 1,2-dichlorobenzene (80 mL). After that, 4-iodoanisole (18.7 g, 80.0 mmol), potassium carbonate (5.5 g, 40.0 mmol), copper powder (1.3 g, 20.0 mmol), and 18-crown-6 ether (5.3 g, 20.0 mmol) were added. The resultant mixture was bubbled with nitrogen for 30 min. The mixture was refluxed for 88 h. After cooling, the solvent was removed in vacuo and the residue was purified by flash chromatography using 25% DCM/hexane to yield N-([1,1′-biphenyl]-2-yl)-N-(4-methoxyphenyl)-[1,1′-biphenyl]-2-amine (7.4 g, 87% yield) as a colorless oil.

後処理

  1. customToluene (100 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. temperaturerefluxed for 21 h
  5. temperatureAfter cooling
  6. filtrationthe reaction mixture was filtered through a silica pad
  7. washwashed with 50% DCM/hexane
  8. customThe solvent was removed in vacuo
  9. dissolutionThe residue was dissolved in 1,2-dichlorobenzene (80 mL)
  10. customThe resultant mixture was bubbled with nitrogen for 30 min
  11. temperatureThe mixture was refluxed for 88 h
  12. temperatureAfter cooling
  13. customthe solvent was removed in vacuo
  14. customthe residue was purified by flash chromatography

出典と根拠

ORDレコード
ord-db4f7770ffb54d8c8591a95041d560b4
出典データセット
uspto-grants-2016_03
特許番号
US09293712B2

関連ノート

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