Aluminium lithium hydride → 7-fluoro-3,4-dihydro-1,5-benzothiazepin-5(2H)-amine

HRID 350778ノート

反応式

HRID 350778 の反応式
[F:1][C:2]1[CH:3]=[CH:4][C:5]2[S:11][CH2:10][CH2:9][CH2:8][N:7]([N:12]=O)[C:6]=2[CH:14]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-]>C1COCC1>[F:1][C:2]1[CH:3]=[CH:4][C:5]2[S:11][CH2:10][CH2:9][CH2:8][N:7]([NH2:12])[C:6]=2[CH:14]=1

参加物

4

反応物 2

HCID 21226445Aluminium lithium hydrideHCID 220367967-Fluoro-5-nitroso-2,3,4,5-tetrahydro-1,5-benzothiazepine

生成物 1

HCID 220368027-fluoro-3,4-dihydro-1,5-benzothiazepin-5(2H)-amine収率 112.6%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

7-fluoro-5-nitroso-2,3,4,5-tetrahydro-1,5-benzothiazepine (449 mg, 2.11 mmol) was suspended in THF (1 mL of freshly distilled) and cooled to 0° C. in an ice bath. Lithium aluminum hydride (80 mg, 2.11 mmol) was added in a portion-wise fashion. The flask was removed from the ice bath and allowed to warm to room temperature and was stirred for 2 hours. Water (0.08 mL) was added and stirred for 10 minutes. 15% sodium hydroxide (0.08 mL) was added stirred for 10 minutes. Water (0.024 mL) was added and stirred for 10 minutes. The reaction was extracted with dichloromethane (2×25 mL). The organics were concentrated to a residue, then taken up in minimal amount of dichloromethane and then hydrogen chloride in ether (1 M) was added until precipatation formed, the precipatate was filtered off to give 7-fluoro-3,4-dihydro-1,5-benzothiazepin-5(2H)-amine (471 mg, 95%). 1H NMR (CD-3OD, 300 MHz): δ 7.59 (t, 1H, J=7.5 Hz), 7.28 (d, 1H, J=9.9 Hz), 7.00 (t, 1H, J=8.2 Hz), 3.52 (t, 1H, J=7.5 Hz), 2.92–2.86 (m, 1H), 2.72–2.70 (m, 2H), 2.40–2.31 (m, 1H), 2.2–2.18 (m, 2H) ppm.

後処理

  1. distillationof freshly distilled) and
  2. customThe flask was removed from the ice bath
  3. temperatureto warm to room temperature
  4. additionWater (0.08 mL) was added
  5. stirringstirred for 10 minutes
  6. addition15% sodium hydroxide (0.08 mL) was added
  7. stirringstirred for 10 minutes
  8. additionWater (0.024 mL) was added
  9. stirringstirred for 10 minutes
  10. extractionThe reaction was extracted with dichloromethane (2×25 mL)
  11. concentrationThe organics were concentrated to a residue
  12. additionhydrogen chloride in ether (1 M) was added until precipatation
  13. customformed
  14. filtrationthe precipatate was filtered off

出典と根拠

ORDレコード
ord-e4d211b2ad77433f9fc47917c774b142
出典データセット
uspto-grants-2007_02
特許番号
US07183282B2

反応ノート

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