Ammonia → 1-(6-Chloro-2,3-dihydrobenzo[b][1,4]dioxin-8-yl)ethanamine

HRID 2426033ノート

反応式

HRID 2426033 の反応式
[Cl:1][C:2]1[CH:11]=[C:10]([C:12](=O)[CH3:13])[C:5]2[O:6][CH2:7][CH2:8][O:9][C:4]=2[CH:3]=1.[NH3:15].C(O)C.[BH4-].[Na+]>CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-]>[Cl:1][C:2]1[CH:11]=[C:10]([CH:12]([NH2:15])[CH3:13])[C:5]2[O:6][CH2:7][CH2:8][O:9][C:4]=2[CH:3]=1

参加物

6

反応物 4

HCID 222AmmoniaHCID 702EthanolHCID 4311764Sodium borohydrideHCID 587072841-(6-Chloro-2,3-dihydrobenzo[b][1,4]dioxin-8-yl)ethanone

生成物 1

HCID 587073121-(6-Chloro-2,3-dihydrobenzo[b][1,4]dioxin-8-yl)ethanamine収率 61%

試薬・触媒・溶媒 1

HCID 11026Titanium isopropoxide触媒

反応条件

温度
0 °C

実験手順

1-(6-Chloro-2,3-dihydrobenzo[b][1,4]dioxin-8-yl)ethanone (248 mg, 1.17 mmol), titanium(IV) isopropoxide (0.84 mL, 2.33 mmol) and 2 M solution of ammonia in ethanol (2.90 mL, 5.83 mmol) were stirred at room temperature for 6 h. The reaction was cooled to 0° C. and sodium borohydride was added portionwise during 10 min. (0.66 mg, 1.76 mmol); the resultant mixture was stirred at rt for an additional 3 h. The reaction was quenched by pouring it into ammonium hydroxide (2 M, 20 mL), the precipitate that formed was filtered off and washed with ethyl acetate (10 mL×3). The organic layer was separated and the remaining aqueous layer was extracted with ethyl acetate (10 mL×2). The combined organic extracts were washed with 1 M HCl (10 mL). The acidic aqueous extracts were washed with ethyl acetate (25 mL), then treated with aqueous sodium hydroxide (2 M) to pH 10-12, and extracted with ethyl acetate (25 mL×3). The combined organic extracts were washed with brine (10 mL), dried (Na2SO4), and concentrated in vacuo to afford the desired product (130 mg, 61% yield). 1H NMR (400 MHz, CDCl3): δ 6.87 (d, 1H), 6.75 (d, 1H), 4.24 (m, 5H), 1.35 (d, 3H).

後処理

  1. customThe reaction was quenched
  2. additionby pouring it into ammonium hydroxide (2 M, 20 mL)
  3. customthe precipitate that formed
  4. filtrationwas filtered off
  5. washwashed with ethyl acetate (10 mL×3)
  6. customThe organic layer was separated
  7. extractionthe remaining aqueous layer was extracted with ethyl acetate (10 mL×2)
  8. washThe combined organic extracts were washed with 1 M HCl (10 mL)
  9. washThe acidic aqueous extracts were washed with ethyl acetate (25 mL)
  10. additiontreated with aqueous sodium hydroxide (2 M) to pH 10-12
  11. extractionextracted with ethyl acetate (25 mL×3)
  12. washThe combined organic extracts were washed with brine (10 mL)
  13. dry with materialdried (Na2SO4)
  14. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-ee3fe06b79c74c9ab87b8c08034ca2e8
出典データセット
uspto-grants-2011_06
特許番号
US07968538B2

反応ノート

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