Stannous chloride dihydrate → HCID 72706949、化合物

HRID 59729ノート

反応式

HRID 59729 の反応式
[Cl:1][C:2]1[CH:3]=[N+:4]([O-:46])[CH:5]=[C:6]([Cl:45])[C:7]=1[CH2:8][C@@H:9]([C:30]1[CH:35]=[CH:34][C:33]([O:36][CH:37]([F:39])[F:38])=[C:32]([O:40][CH2:41][CH:42]2[CH2:44][CH2:43]2)[CH:31]=1)[O:10][C:11]([C:13]1[N:14]([S:18]([C:21]2[CH:26]=[CH:25][C:24]([N+:27]([O-])=O)=[CH:23][CH:22]=2)(=[O:20])=[O:19])[CH:15]=[CH:16][CH:17]=1)=[O:12].O.O.[Sn](Cl)Cl>C1COCC1>[NH2:27][C:24]1[CH:23]=[CH:22][C:21]([S:18]([N:14]2[CH:15]=[CH:16][CH:17]=[C:13]2[C:11]([O:10][C@H:9]([C:30]2[CH:35]=[CH:34][C:33]([O:36][CH:37]([F:38])[F:39])=[C:32]([O:40][CH2:41][CH:42]3[CH2:44][CH2:43]3)[CH:31]=2)[CH2:8][C:7]2[C:2]([Cl:1])=[CH:3][N+:4]([O-:46])=[CH:5][C:6]=2[Cl:45])=[O:12])(=[O:20])=[O:19])=[CH:26][CH:25]=1

参加物

4

反応物 2

HCID 61436Stannous chloride dihydrate2 回HCID 86703836(S)-3,5-dichloro-4-(2-(3-(cyclopropylmethoxy)-4-(difluoromethoxy)phenyl)-2-(1-(4-nitrophenylsulfonyl)-1H-pyrrole-2-carbonyloxy)-ethyl)pyridine 1-oxide

生成物 1

HCID 72706949HCID 72706949、化合物収率 51.1%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
45 °C

実験手順

A mixture of (S)-3,5-dichloro-4-(2-(3-(cyclopropylmethoxy)-4-(difluoromethoxy)phenyl)-2-(1-(4-nitrophenylsulfonyl)-1H-pyrrole-2-carbonyloxy)-ethyl)pyridine 1-oxide (Int. 6) (424 mg, 0.607 mmol) and tin(II) chloride dihydrate (548 mg, 2.428 mmol) in THF (40 ml) was heated at 45° C. for 2 hours. Additional tin(II) chloride dihydrate (1.644 g, 7.284 mmol) was added in 3 portion over 3 hours at 60° C., and the resulting mixture was heated to reflux overnight. The solvent was removed and the mixture was diluted with ethyl acetate; aqueous sat. NaHCO3 was added and the mixture was filtered through a celite pad. The filtered phases were separated and the organic layer was washed with brine and dried over sodium sulfate; the solvent was removed and the crude was purified by flash chromatography on silica gel column (DCM/MeOH=98/2) affording (S)-4-(2-(1-(4-aminophenylsulfonyl)-1H-pyrrole-2-carbonyloxy)-2-(3-(cyclopropylmethoxy)-4-(difluoromethoxy)-phenyl)ethyl)-3,5-dichloropyridine 1-oxide (Int. 7) (207 mg, 0.310 mmol, MS/ESI+667.96 [MH]+, [αD]=−61.24, c=1, DCM).

後処理

  1. temperaturethe resulting mixture was heated
  2. temperatureto reflux overnight
  3. customThe solvent was removed
  4. additionthe mixture was diluted with ethyl acetate
  5. additionaqueous sat. NaHCO3 was added
  6. filtrationthe mixture was filtered through a celite pad
  7. customThe filtered phases were separated
  8. washthe organic layer was washed with brine
  9. dry with materialdried over sodium sulfate
  10. customthe solvent was removed
  11. customthe crude was purified by flash chromatography on silica gel column (DCM/MeOH=98/2)

出典と根拠

ORDレコード
ord-73c363d06d614eee8b2de7b2d860ed26
出典データセット
uspto-grants-2016_09
特許番号
US09440954B2

反応ノート

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