Diethyl Ether → Diethyl[(4-nitrophenyl)(difluoro)methyl]phosphonate

HRID 511421

反応式

HRID 511421 の反応式
[CH3:1][CH2:2][O:3][P:4]([O:10][CH2:11][CH3:12])([C:6](Br)([F:8])[F:7])=[O:5].I[C:14]1[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[CH:16][CH:15]=1.CCOCC>CN(C=O)C.Cl[Cu]>[N+:20]([C:17]1[CH:18]=[CH:19][C:14]([C:6]([P:4](=[O:5])([O:10][CH2:11][CH3:12])[O:3][CH2:2][CH3:1])([F:8])[F:7])=[CH:15][CH:16]=1)([O-:22])=[O:21]

参加物

6

反応物 3

HCID 3283Diethyl EtherHCID 124951-Iodo-4-nitrobenzeneHCID 144101Bromodifluoromethyl diethylphosphonate

生成物 1

HCID 10881410Diethyl[(4-nitrophenyl)(difluoro)methyl]phosphonate収率 86.4%

試薬・触媒・溶媒 2

HCID 62652Cuprous chloride触媒HCID 6228Dimethylformamide溶媒

実験手順

Under N2, a mixture of bromodifluoromethyl diethylphosphonate (0.427 g, 1.6 mmol) and Cd powder (180 mg, 1.6 mmol) in DMF (0.5 mL) was stirred at room temperature for 2 h. Most of Cd disappeared. 4-Iodo-1-nitrobenzene (249 mg, 1.00 mmol) and CuCl (115 mg, 1.16 mmol) were then added. The mixture was again stirred at room temperature for 3 h. Ether (20 mL) was added to the reaction mixture and the precipitated solids were filtered off and washed with 10 mL of ether. The combined ether layers were washed with NH4Cl (aq), dried over MgSO4, and evaporated to give the title product (267 mg, yield: 86%). 1H NMR (CD3OD, 400 MHz): δ=1.33 (t, J=7.2 Hz, 6 H), 4.20-4.28 (m, 4 H), 7.86 (d, J=8.4 Hz, 2 H), 8.39 (d, J=8.4 Hz, 2 H). MS (ES+): m/z 310.06 [MH+]. HPLC: tR=3.92 min (ZQ3, polar—5 min).

後処理

  1. stirringThe mixture was again stirred at room temperature for 3 h
  2. filtrationthe precipitated solids were filtered off
  3. washwashed with 10 mL of ether
  4. washThe combined ether layers were washed with NH4Cl (aq)
  5. dry with materialdried over MgSO4
  6. customevaporated

出典と根拠

ORDレコード
ord-74edbd9c43fd48d09099dde919adc8eb
出典データセット
uspto-grants-2015_08
特許番号
US09096624B2

関連ノート

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