1,2-Dibromoethane → [1,1':2',1''-Terphenyl]-2-yldi-tert-butylphosphane

HRID 382123

反応式

HRID 382123 の反応式
[Mg].Br[CH2:3][CH2:4]Br.[CH3:6][C:7]1[CH:12]=[CH:11][C:10](C)=[CH:9][C:8]=1[C:14]1[CH:19]=[CH:18][CH:17]=[C:16](C)[CH:15]=1.[C:21]([P:25]([C:27]([CH3:30])([CH3:29])[CH3:28])Cl)([CH3:24])([CH3:23])[CH3:22].[CH2:31]1[CH2:35]OC[CH2:32]1>[Cu]Cl>[C:21]([P:25]([C:27]([CH3:30])([CH3:29])[CH3:28])[C:19]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[C:8]1[C:7]([C:6]2[CH:4]=[CH:3][CH:35]=[CH:31][CH:32]=2)=[CH:12][CH:11]=[CH:10][CH:9]=1)([CH3:24])([CH3:23])[CH3:22]

参加物

7

反応物 5

HCID 78391,2-DibromoethaneHCID 8028Tetrahydrofuran3 回HCID 139566Di-tert-butylchlorophosphineHCID 5462224MagnesiumHCID 110416892,3',5-Trimethyl-1,1'-biphenyl

生成物 1

HCID 9951497[1,1':2',1''-Terphenyl]-2-yldi-tert-butylphosphane収率 26%

試薬・触媒・溶媒 1

HCID 62652Cuprous chloride触媒

実験手順

An oven-dried Schlenk tube was cooled to room temperature under an argon purge, and was charged with magnesium turnings (54 mg, 2.2 mmol), THF (2 mL), and 1,2-dibromoethane (9 μL). The mixture was stirred at room temperature for 15 min, then a solution of 2 (618 mg, 2.0 mmol) in 1 mL THF was added dropwise. The mixture was stirred at rt for 1 h, then the septum was removed from the flask, and copper (I) chloride (283 mg, 2.1 mmol) was added. The tube was capped with the septum and purged with argon for 1 min. The tube was charged with di-t-butylchlorophosphine (0.46 mL, 2.4 mmol) and additional THF (1 mL). The mixture was heated to 60° C. with stirring for 26 h. The mixture was cooled to room temperature and filtered, and the solids were washed with ether/hexanes (50 mL, 1/1 v/v). The organic solution was poured into a separatory funnel and washed with ammonium hydroxide solution (3×50 mL), and brine (50 mL). The organic phase was then dried over anhydrous sodium sulfate, filtered, and concentrated. The crude material was recrystallized from hot methanol to afford 191 mg (26%) of 3 as a white, crystalline solid.

後処理

  1. custompurge
  2. stirringThe mixture was stirred at rt for 1 h
  3. additionwas added
  4. customThe tube was capped with the septum
  5. custompurged with argon for 1 min
  6. temperatureThe mixture was heated to 60° C.
  7. stirringwith stirring for 26 h
  8. temperatureThe mixture was cooled to room temperature
  9. filtrationfiltered
  10. washthe solids were washed with ether/hexanes (50 mL, 1/1 v/v)
  11. additionThe organic solution was poured into a separatory funnel
  12. washwashed with ammonium hydroxide solution (3×50 mL), and brine (50 mL)
  13. dry with materialThe organic phase was then dried over anhydrous sodium sulfate
  14. filtrationfiltered
  15. concentrationconcentrated
  16. customThe crude material was recrystallized from hot methanol

出典と根拠

ORDレコード
ord-dc5b6189dd4c47adb8af69638420fc63
出典データセット
uspto-grants-2001_10
特許番号
US06307087B1

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