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

HRID 581453노트

반응식

HRID 581453 반응식
[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

참가 물질

9

반응물 4

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

생성물 1

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

시약·촉매·용매 4

HCID 167845palladium(II) acetate촉매HCID 111,2-Dichloroethane용매HCID 3283Diethyl Ether용매HCID 8003Pentane용매2회

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-8f6af12a08ad46deb152294c38c5d79b
출처 데이터셋
uspto-grants-1999_07
특허 번호
US05919984

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