Iodine → [5-Amino-2-(morpholin-4-yl)phenyl]methanol

HRID 449810

反応式

HRID 449810 の反応式
[BH4-].[Na+].O1CCCC1.[NH2:8][C:9]1[CH:10]=[CH:11][C:12]([N:18]2[CH2:23][CH2:22][O:21][CH2:20][CH2:19]2)=[C:13]([C:15](O)=[O:16])[CH:14]=1.II>CO>[NH2:8][C:9]1[CH:10]=[CH:11][C:12]([N:18]2[CH2:19][CH2:20][O:21][CH2:22][CH2:23]2)=[C:13]([CH:14]=1)[CH2:15][OH:16]

参加物

6

反応物 4

HCID 807Iodine2 回HCID 8028Tetrahydrofuran2 回HCID 6137005-Amino-2-morpholinobenzenecarboxylic acidHCID 4311764Sodium borohydride

生成物 1

HCID 23136616[5-Amino-2-(morpholin-4-yl)phenyl]methanol収率 72%

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

反応条件

温度
0 °C

実験手順

A 50 mL two necked round bottom flask was fitted with a magnetic stirrer bar and a dropping funnel. A suspension of NaBH4 in tetrahydrofuran (100 mg, 2.4 mmol/10 mL) was added, followed by 5-amino-2-morpholinobenzenecarboxylic acid (222 mg, 1.0 mmol) in one portion. A reflux condenser was fitted and the reaction mixture was cooled to 0° C. under nitrogen atmosphere. A solution of iodine in tetrahydrofuran (250 mg, 1.0 mmol/15 mL) was added dropwise to the reaction mixture. After iodine addition was completed and gas evolution had ceased, the reaction mixture was heated at reflux for 6 hours and left stirring at room temperature overnight. Methanol was added slowly until the mixture became clear. The resulting solution stirred at room temperature for 30 minutes then solvent was removed under reduced pressure. The residue was dissolved in 20% KOH (30 mL), stirred for 4 hours and extracted with dichloromethane (3×30 mL). The combined organic extracts were washed with brine, dried over anhydrous Na2SO4 and concentrated to give 5-amino-2-morpholinobenzyl alcohol as an off-white solid (150 mg, 72% yield). 1H NMR (300 MHz, CDCl3) δ 7.05 (d, J=8.7 Hz, 1H), 6.59 (dd, J=8.4, 2.7 Hz, 1H), 6.49 (d, J=2.7 Hz, 1H), 5.51 (br s, 1H), 4.71 (s, 2H), 3.84 (t, J=5.1 Hz, 4H), 3.60 (br s, 2H), 2.91 (t, J=5.1 Hz, 4H). LC-ESI-MS (method B): rt 2.31 min.; m/z 209.2 [M+H]+.

後処理

  1. additionwas added
  2. customA reflux condenser was fitted
  3. temperaturethe reaction mixture was heated
  4. temperatureat reflux for 6 hours
  5. waitleft
  6. stirringThe resulting solution stirred at room temperature for 30 minutes
  7. customsolvent was removed under reduced pressure
  8. dissolutionThe residue was dissolved in 20% KOH (30 mL)
  9. stirringstirred for 4 hours
  10. extractionextracted with dichloromethane (3×30 mL)
  11. washThe combined organic extracts were washed with brine
  12. dry with materialdried over anhydrous Na2SO4
  13. concentrationconcentrated

出典と根拠

ORDレコード
ord-be5ad3d898884ab9a41bd1b2d6fe9604
出典データセット
uspto-grants-2013_07
特許番号
US08486941B2

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