Hydrochloric Acid → 3-Bromo-5-methoxybenzenemethanamine

HRID 564454ノート

反応式

HRID 564454 の反応式
[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([O:11][CH3:12])[CH:10]=1)[C:5]([NH2:7])=O.S(C)C.CCO.Cl>C1COCC1.CO>[Br:1][C:2]1[CH:3]=[C:4]([CH2:5][NH2:7])[CH:8]=[C:9]([O:11][CH3:12])[CH:10]=1

参加物

7

反応物 4

HCID 313Hydrochloric Acid2 回HCID 702EthanolHCID 1068Dimethyl SulfideHCID 578133713-Bromo-5-methoxybenzamide

生成物 1

HCID 534144413-Bromo-5-methoxybenzenemethanamine収率 82.5%

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of 3-bromo-5-(methyloxy)benzamide (4.00 g, 17.4 mmol) in THF (60 mL), BH3.Me2S (2.64 g, 34.8 mol) was added at 0° C. After the end of the addition, the reaction mixture was kept refluxing overnight (monitored by TLC). After cooling to room temperature, EtOH was cautiously added to the reaction mixture. When there no more air bubbles appeared, the mixture was acidified with 1N HCl to pH=2. Then the mixture was stirred at 50° C. for 4 h, filtered and the filter rinsed with water (20 mL×2). The filtrate was washed with EtOAc (50 mL×3). After addition of 2N NaOH (pH=10), the filtrate was extracted with EtOAc (100 mL×3). The combined extracts were washed with brine, dried over anhydrous sodium sulfate and concentrated to give a mixture of solid and oil. MeOH (10 mL) and conc. HCl (10 mL) were added and concentrated to afford crude material as a white solid. Recrystallization from MeOH-Et2O gave the captioned product (3.10 g, 71%), {[3-bromo-5-(methyloxy)phenyl]methyl}amine, as colorless fine needles. 1H NMR (400 MHz, D2O): δ 7.12-7.09 (m, 2 H), 6.86 (s, 1 H), 3.98 (s, 2 H), 3.69 (s, 3 H); 13C NMR (100 MHz, D2O): δ160.2, 135.8, 124.2, 123.0, 117.8, 114.0, 55.8, 42.5; HPLC: retention time: 5.452 min; purity: 97.4% (HPLC).

後処理

  1. additionAfter the end of the addition
  2. temperaturethe reaction mixture was kept refluxing overnight (monitored by TLC)
  3. filtrationfiltered
  4. washthe filter rinsed with water (20 mL×2)
  5. washThe filtrate was washed with EtOAc (50 mL×3)
  6. additionAfter addition of 2N NaOH (pH=10)
  7. extractionthe filtrate was extracted with EtOAc (100 mL×3)
  8. washThe combined extracts were washed with brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationconcentrated
  11. customto give
  12. additiona mixture of solid and oil
  13. concentrationconcentrated
  14. customto afford crude material as a white solid
  15. customRecrystallization from MeOH-Et2O

出典と根拠

ORDレコード
ord-b399e24d48554fd7b4f4592e80562d11
出典データセット
uspto-grants-2011_11
特許番号
US08067408B2

反応ノート

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