Ethyl Acetate → Methyl 5-amino-1-bromo-indan carboxylate

HRID 507090ノート

反応式

HRID 507090 の反応式
[Br:1]N1C(=O)CCC1=O.COC([C:13]1[CH:14]=[C:15]2[C:19](=[CH:20][C:21]=1[NH2:22])[CH2:18][CH2:17][CH2:16]2)=O.[C:23]([O:26][CH2:27]C)(=[O:25])C>C(O)(=O)C>[NH2:22][C:21]1[CH:20]=[C:19]2[C:15](=[CH:14][CH:13]=1)[C:16]([Br:1])([C:23]([O:26][CH3:27])=[O:25])[CH2:17][CH2:18]2

参加物

5

反応物 3

HCID 8857Ethyl AcetateHCID 67184N-bromobutanimideHCID 59379136methyl 6-amino-2,3-dihydro-1H-indene-5-carboxylate

生成物 1

HCID 67422511Methyl 5-amino-1-bromo-indan carboxylate収率 95%

試薬・触媒・溶媒 1

HCID 176Acetic Acid溶媒

実験手順

Add N-bromosuccinimide (1.87 g, 10.5 mmol) to methyl 6-amino-indan-5-carboxylate (1.82 g, 9.53 mmol) (Example 49, Step 3) in acetic acid (9.3 mL). Stir the mixture at room temperature for 1 h. Pour the mixture into ice water and add ethyl acetate. Separate the layers and wash the organic phase with saturated NaHCO3 and brine and dry over sodium sulfate. Remove the solvent under reduced pressure. Purify with silica gel cartridge, eluting with hexanes/ethyl acetate to afford methyl 5-amino-1-bromo-indan carboxylate (2.45 g, 95%): MS (ES+): 271, 272 (M+H). Add methyl boronic acid (1.6 g, 26.7 mmol), cesium fluoride (4.6 g, 30.22 mmol) and 1-bis(diphenylphosphinoferrocene) palladium chloride (727 mg, 0.89 mmol) to methyl 5-amino-1-bromo-indan carboxylate (2.40 g, 8.89 mmol) in dioxane (60 ml), and stir at 90° C. for 12 h. Partition between water and ethyl acetate. Extract with more ethyl acetate and then combine the organic phases. Dry over sodium sulfate and remove the solvent under reduced pressure. Purify with silica gel cartridge, eluting with hexanes/ethyl acetate to afford the titled compound (1.73 g, 95%). MS (ES+): 206 (M+H).

後処理

  1. customSeparate the layers
  2. washwash the organic phase with saturated NaHCO3 and brine
  3. dry with materialdry over sodium sulfate
  4. customRemove the solvent under reduced pressure
  5. customPurify with silica gel cartridge
  6. washeluting with hexanes/ethyl acetate

出典と根拠

ORDレコード
ord-55be49a00df34ecbbf468c78df5e63a5
出典データセット
uspto-grants-2010_08
特許番号
US07786108B2

反応ノート

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