Sodium Iodide → Bis(diphenylphosphine)methane monooxide

HRID 581452ノート

反応式

HRID 581452 の反応式
[CH:1]1[CH:2]=[CH:3][C:4]([P:7]([C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)[CH2:8][P:9]([C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=2)=[CH:5][CH:6]=1.BrCCBr.[OH-:32].[Na+].[Na+].[I-]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.ClCCl>[P:7]([CH2:8][P:9]([C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:32])([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[C:4]1[CH:3]=[CH:2][CH:1]=[CH:6][CH:5]=1

参加物

7

反応物 4

HCID 5238Sodium IodideHCID 78391,2-DibromoethaneHCID 14798Sodium HydroxideHCID 74952Bis(diphenylphosphino)methane

生成物 1

HCID 303894Bis(diphenylphosphine)methane monooxide

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 6344Dichloromethane溶媒

実験手順

A mixture of palladium acetate (5 mg; 2.2×10-2 mmol), dppm (2.00 g; 5.21 mmol), 1,2-dibromoethane (2.0 g; 10.64 mmol), and dichloromethane (10 mL) was stirred for 20 minutes. To this solution, aqueous NaOH (20% by weight; 6 mL) containing NaI (40 mg; 0.27 mmol) was added and the mixture was vigorously stirred under reflux for 4 hours. The organic phase was filtered through a silica plug which was then washed with CH2Cl2 /AcOEt (3:1 by volume). The combined organic solutions were evaporated to dryness. The solid residue was dissolved in the minimum amount of boiling CH2Cl2, the warm solution was treated with ether (100 mL; portionwise) and left at room temperature for 2 hours. Slightly yellowish fluffy needles of spectroscopically and TLC pure dppmO were separated, washed with ether, and dried under vacuum. The yield was 1.53 g (74%). 1H NMR (CDCl3, 20° C.), δ: 3.1 (d, 2H, J=12.7 Hz, CH2); 7.1-7.9 (m, 20H, Ph). 31P NMR (CDCl3, 20° C.), δ: -26.5 (d, 1P, JP-P =50.5 Hz, PPh2); 29.8 (d, 1P, JP-P =50.5 Hz, P(O)Ph2).

後処理

  1. additionwas added
  2. stirringthe mixture was vigorously stirred
  3. temperatureunder reflux for 4 hours
  4. filtrationThe organic phase was filtered through a silica plug which
  5. washwas then washed with CH2Cl2 /AcOEt (3:1 by volume)
  6. customThe combined organic solutions were evaporated to dryness
  7. dissolutionThe solid residue was dissolved in the minimum amount of boiling CH2Cl2
  8. additionthe warm solution was treated with ether (100 mL
  9. waitportionwise) and left at room temperature for 2 hours
  10. customSlightly yellowish fluffy needles of spectroscopically and TLC pure dppmO were separated
  11. washwashed with ether
  12. customdried under vacuum

出典と根拠

ORDレコード
ord-789bcb6607c249288db7e3cad7ad98e8
出典データセット
uspto-grants-1999_07
特許番号
US05919984

反応ノート

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