Bromotrimethylsilane → [2-Phenyl-1-(thiophene-2-sulfonylamino)-ethyl]phosphonic acid

HRID 854408ノート

反応式

HRID 854408 の反応式
C([O:3][P:4]([CH:9]([NH:17][S:18]([C:21]1[S:22][CH:23]=[CH:24][CH:25]=1)(=[O:20])=[O:19])[CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)(=[O:8])[O:5]CC)C.Br[Si](C)(C)C>ClCCl>[C:11]1([CH2:10][CH:9]([P:4](=[O:3])([OH:5])[OH:8])[NH:17][S:18]([C:21]2[S:22][CH:23]=[CH:24][CH:25]=2)(=[O:19])=[O:20])[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

参加物

4

反応物 2

HCID 76113BromotrimethylsilaneHCID 228909322-Phenyl-1-(thiophene-2-sulfonylamino)-ethyl-phosphonic Acid Diethyl Ester

生成物 1

HCID 22179290[2-Phenyl-1-(thiophene-2-sulfonylamino)-ethyl]phosphonic acid収率 81.9%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

To a solution of diethyl phosphonate (xii) (745 mg; 1.8 mmol) in dichloromethane (8 mL) at 0° C. was slowly added bromotrimethylsilane (2 mL; 15.2 mmol). The reaction was gradually warmed to room temperature and the following day the solution was evaporated. The residue was redissolved in dichloromethane (10 mL), evaporated and the process repeated once more. Methanol (10 mL) was added to the residue and the solution stirred at room temperature for 30 minutes, then the solution was filtered and concentrated. The oily residue was triturated with 1:1 ether-hexanes and the orange solid collected by filtration. Finally, the orange solid was boiled in dichloromethane (5 mL), cooled and filtered to yield pure phosphonic acid (xiii) (512 mg, 80%) as a colorless solid: 1H NMR (400 MHz, CD3OD) δH 2.71 (dt, J=14, 10 Hz, 1H, CHPh), 3.13 (ddd, J=4, 8, 14 Hz, 1H, CHPh), 3.89 (ddd, J=4, 10, 14 Hz, NCHP), 6.86 (dd, J=3.5, 5 Hz, 1H, Ar—H), 7.07-7.15 (m, 6H, Ar—H), 7.53 (dd, J=1.5, 5 Hz, 1H, Ar—H).

後処理

  1. customat 0° C.
  2. customthe following day the solution was evaporated
  3. dissolutionThe residue was redissolved in dichloromethane (10 mL)
  4. customevaporated
  5. additionMethanol (10 mL) was added to the residue
  6. filtrationthe solution was filtered
  7. concentrationconcentrated
  8. customThe oily residue was triturated with 1:1 ether-hexanes
  9. filtrationthe orange solid collected by filtration
  10. temperaturecooled
  11. filtrationfiltered

出典と根拠

ORDレコード
ord-fcfa1e7f55fd4f2da7c8b36426731c8d
出典データセット
uspto-grants-2007_08
特許番号
US07259172B2

反応ノート

読み込み中…