Dichloromethane → [3-(Diphenylphosphanyl)propyl](oxo)diphenyl-lambda~5~-phosphane

HRID 581453ノート

反応式

HRID 581453 の反応式
[CH:1]1[CH:2]=[CH:3][C:4]([P:7]([C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[CH2:8][CH2:9][CH2:10][P:11]([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)=[CH:5][CH:6]=1.BrCCBr.[OH-:34].[Na+].C(Cl)Cl>ClCCCl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CCCCC.CCOCC>[P:7]([CH2:8][CH2:9][CH2:10][P:11]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1)=[O:34])([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:4]1[CH:3]=[CH:2][CH:1]=[CH:6][CH:5]=1

参加物

9

反応物 4

HCID 6344DichloromethaneHCID 78391,2-DibromoethaneHCID 14798Sodium HydroxideHCID 812191,3-Bis(diphenylphosphino)propane

生成物 1

HCID 3336369[3-(Diphenylphosphanyl)propyl](oxo)diphenyl-lambda~5~-phosphane

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒HCID 111,2-Dichloroethane溶媒HCID 3283Diethyl Ether溶媒HCID 8003Pentane溶媒2 回

実験手順

Palladium acetate (10 mg; 4.45×10-2 mmol), dppp (5.00 g; 12.14 mmol), and 1,2-dibromoethane (3.4 g; 18.9 mmol) were dissolved in 1,2-dichloroethane (15 mL). To this solution, aqueous NaOH (20% by weight; 10 mL) was added and the biphasic mixture was vigorously stirred under reflux for 6 hours until the originally yellow mixture turned pale yellow. The organic phase was filtered through a silica column which was then washed with CH2Cl2 /AcOEt (5:3 by volume) until the yellow band was about to come out. The combined organic solutions were evaporated to give a colorless oily residue. The oil was mixed with CH2Cl2 (2 mL) and ether (5 mL), and then treated with pentane (10 mL) and left for 1.5 hours. More pentane (50 ml) was added, and in 2 hours the fluffy white needles of dpppO were separated and dried under vacuum. The yield was 3.80 g (73%). 1H NMR (CDCl3, 20° C.), δ: 1.8 (m, 2H, CH2); 2.2 (m, 2H, CH2); 2.4 (m, 2H, CH2); 7.2-7.7 (m, 20H, Ph). 31P NMR (CDCl3, 20° C.), δ: -17.2 (s, 1P, PPh2); 32.0 (s, 1P, P(O)Ph2).

後処理

  1. temperatureunder reflux for 6 hours until the originally yellow mixture
  2. filtrationThe organic phase was filtered through a silica column which
  3. washwas then washed with CH2Cl2 /AcOEt (5:3 by volume) until the yellow band
  4. customThe combined organic solutions were evaporated
  5. customto give a colorless oily residue
  6. customin 2 hours the fluffy white needles of dpppO were separated
  7. customdried under vacuum

出典と根拠

ORDレコード
ord-8f6af12a08ad46deb152294c38c5d79b
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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