Sodium Carbonate → 7-bromo-2,3-dihydro-1,4-benzodioxin-6-amine

HRID 639013ノート

反応式

HRID 639013 の反応式
[O:1]1[C:6]2[CH:7]=[CH:8][C:9]([NH2:11])=[CH:10][C:5]=2[O:4][CH2:3][CH2:2]1.[Br:12]N1C(=O)CCC1=O.C(=O)([O-])[O-].[Na+].[Na+]>O1CCCC1.S(=O)(=O)(O)O>[Br:12][C:8]1[C:9]([NH2:11])=[CH:10][C:5]2[O:4][CH2:3][CH2:2][O:1][C:6]=2[CH:7]=1

参加物

6

反応物 3

HCID 10340Sodium CarbonateHCID 67184N-bromobutanimideHCID 891481,4-Benzodioxan-6-ylamine

生成物 1

HCID 49832297-bromo-2,3-dihydro-1,4-benzodioxin-6-amine収率 115.6%

試薬・触媒・溶媒 2

HCID 1118Sulfuric Acid触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

A solution of 2,3-dihydro-benzo[1,4]dioxin-6-ylamine (80 g, 530 mmol, 1 eq) in tetrahydrofuran (1000 mL) at −78° C. was treated with concentrated sulfuric acid (50 drops) then N-bromosuccinimide (94.2 g, 530 mmol, 1 eq) was added over 0.5 hour. After the addition the mixture was stirred at −78° C. for 1 hour then treated with solid sodium carbonate (12 g, 113 mmol, 0.21 eq). The mixture was evaporated and the residue partitioned between ether and water. The organic extract was dried, filtered and evaporated to give to oil that was chromatographed on silica gel eluting with dichloromethane to afford oil (141 g, 92%). LC/MS (ES) m/z 230 (MH+ 91%); 1H-NMR (400 MHz, d6-DMSO), 6.85 (1H, s, CHCNH2), 6.34 (1H, s, CHCBr), 4.79 (2H, s, NH2), 4.16 (4H, dd, J=16, 2×(CH2O))

後処理

  1. additionAfter the addition the mixture
  2. customThe mixture was evaporated
  3. customthe residue partitioned between ether and water
  4. extractionThe organic extract
  5. customwas dried
  6. filtrationfiltered
  7. customevaporated
  8. customto give to oil that
  9. customwas chromatographed on silica gel eluting with dichloromethane

出典と根拠

ORDレコード
ord-5f69fbe819ab4a0f98d02cfe685acf79
出典データセット
uspto-grants-2010_04
特許番号
US07691850B2

反応ノート

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