Hydrochloric Acid → benzyl N-[(2S)-2-hydroxy-3-(4-methylpiperazin-1-yl)propyl]carbamate

HRID 2364712ノート

反応式

HRID 2364712 の反応式
[CH2:1]([O:8][C:9]([NH:11][CH2:12][C@H:13]([OH:28])[CH2:14][N:15]1[CH2:20][CH2:19][N:18]([C:21](OC(C)(C)C)=O)[CH2:17][CH2:16]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.C=O.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCl.O1CCOCC1.O.C(O)(=O)C>[OH:28][C@H:13]([CH2:14][N:15]1[CH2:20][CH2:19][N:18]([CH3:21])[CH2:17][CH2:16]1)[CH2:12][NH:11][C:9](=[O:10])[O:8][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

9

反応物 4

HCID 313Hydrochloric AcidHCID 712FormaldehydeHCID 5049666Sodium triacetoxyborohydrideHCID 68107178tert-butyl 4-[(2S)-3-benzyloxycarbonylamino-2-hydroxy-propyl]piperazine-1-carboxylate

生成物 1

HCID 68106686benzyl N-[(2S)-2-hydroxy-3-(4-methylpiperazin-1-yl)propyl]carbamate収率 74%

試薬・触媒・溶媒 4

HCID 176Acetic Acid溶媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒2 回HCID 312751,4-Dioxane溶媒

実験手順

Tert-butyl 4-[(2S)-3-benzyloxycarbonylamino-2-hydroxy-propyl]piperazine-1-carboxylate 21a (1.45 g, 3.70 mmol) was dissolved in 30 mL of dichloromethane followed by the addition of 20 mL of a 4 M solution of hydrogen chloride in dioxane. The reaction solution was stirred for 0.5 hours and concentrated under reduced pressure. The residue was added with 40 mL of dichloromethane, formaldehyde (222 mg, 7.40 mmol) and 0.1 mL of acetic acid successively. The resulting solution was stirred for 0.5 hours followed by the addition of sodium triacetoxyborohydride (2.35 g, 11.10 mmol), stirred for another 12 hours. The resulting solution was added with 50 mL of water and extracted with dichloromethane (50 mL×3). The combined organic phase was washed with saturated sodium chloride solution (50 mL×3), then dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain the title compound benzyl N-[(2S)-2-hydroxy-3-(4-methylpiperazin-1-yl)propyl]carbamate 21b (840 mg, yield: 74.0%) as a yellow oil.

後処理

  1. concentrationconcentrated under reduced pressure
  2. stirringThe resulting solution was stirred for 0.5 hours
  3. stirringstirred for another 12 hours
  4. extractionextracted with dichloromethane (50 mL×3)
  5. washThe combined organic phase was washed with saturated sodium chloride solution (50 mL×3)
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationthe filtrate was concentrated under reduced pressure
  9. customThe resulting residue was purified by silica gel column chromatography

出典と根拠

ORDレコード
ord-6149c643d7d342da880240d2faec2616
出典データセット
uspto-grants-2014_04
特許番号
US08691822B2

反応ノート

読み込み中…