Hydrochloric Acid → Benzenemethanamine, 2-(2,3-dihydro-1H-indol-1-yl)-, hydrochloride (1:1)

HRID 371488ノート

反応式

HRID 371488 の反応式
[N:1]1([C:10]2[CH:17]=[CH:16][CH:15]=[CH:14][C:11]=2[C:12]#[N:13])[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[CH2:3][CH2:2]1.[ClH:18].[OH-].[Na+]>O1CCCC1.CCOCC>[ClH:18].[N:1]1([C:10]2[CH:17]=[CH:16][CH:15]=[CH:14][C:11]=2[CH2:12][NH2:13])[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[CH2:3][CH2:2]1

参加物

6

反応物 3

HCID 313Hydrochloric Acid2 回HCID 14798Sodium HydroxideHCID 133247142-(2,3-Dihydro-1H-indol-1-yl)benzonitrile

生成物 1

HCID 13324720Benzenemethanamine, 2-(2,3-dihydro-1H-indol-1-yl)-, hydrochloride (1:1)収率 67.3%

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

A solution of 17.18 g (0.078 mole) of 2(1-indolinyl)benzonitrile of Example 1a in 150 ml dry tetrahydrofuran (THF) was added dropwise to a rapidly stirred ice cold solution of BH3 in THF (236 ml of 1M solution; 0.236 mole) under nitrogen. At the end of the addition the resultant solution was permitted to warm to room temperature and stir for 3 hours and then heated at reflux for 50 minutes. The product was then cooled to 0° C., treated dropwise with 6N HCl (100 ml), and permitted to stand overnight (about 16 hours) at room temperature. The reaction mixture was cooled to 0° C. and made basic using solid NaOH. The resulting aqueous layer was extracted with ether (200 ml) and the combined organic portions were washed twice with brine (200 ml portions), dried over K2CO3, and concentrated to afford 21.1 g of crude free base. The free amine was dissolved in dry ether (300 ml), cooled to 0° C., and treated with gaseous HCl. The resulting salt was filtered, washed with dry ether (300 ml), and dried under vacuum at 40° C. thus affording 19.25 g (94.4%) of crude salt, m.p. 226°-228° C. Recrystallization of 15.59 g of the crude salt from methanol-ether afforded 10.49 g (67.3% recovery) of 2-(1-indolinyl) benzenemethanamine hydrochloride, m.p. 231°-232° C.

後処理

  1. temperatureheated
  2. temperatureat reflux for 50 minutes
  3. temperatureThe product was then cooled to 0° C.
  4. waitto stand overnight
  5. custom(about 16 hours)
  6. customat room temperature
  7. temperatureThe reaction mixture was cooled to 0° C.
  8. extractionThe resulting aqueous layer was extracted with ether (200 ml)
  9. washthe combined organic portions were washed twice with brine (200 ml portions)
  10. dry with materialdried over K2CO3
  11. concentrationconcentrated
  12. customto afford 21.1 g of crude free base
  13. temperaturecooled to 0° C.
  14. filtrationThe resulting salt was filtered
  15. washwashed with dry ether (300 ml)
  16. customdried under vacuum at 40° C.
  17. customthus affording 19.25 g (94.4%) of crude salt, m.p. 226°-228° C
  18. customRecrystallization of 15.59 g of the crude salt from methanol-ether

出典と根拠

ORDレコード
ord-d0f8354959034acc9d666bd4ecce57b9
出典データセット
uspto-grants-1985_07
特許番号
US04532333

反応ノート

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